Blow molded thermoplastic composition

ABSTRACT

Components formed of blow molded thermoplastic compositions are described. The blow molded thermoplastic compositions exhibit high strength and flexibility. Methods for forming the thermoplastic compositions are also described. Formation methods include dynamic vulcanization of a composition that includes an impact modifier dispersed throughout a polyarylene sulfide. A crosslinking agent is combined with the other components of the composition following dispersal of the impact modifier. The crosslinking agent reacts with the impact modifier to form crosslinks within and among the polymer chains of the impact modifier. The compositions can exhibit excellent physical characteristics at extreme temperatures and can be used to form, e.g., tubular member such as pipes and hoses and fibers.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims filing benefit of U.S. Provisional PatentApplication Ser. No. 61/623,618 having a filing date of Apr. 13, 2012,U.S. Provisional Patent Application Ser. No. 61/665,423 having a filingdate of Jun. 28, 2012, U.S. Provisional Patent Application Ser. No.61/678,370 having a filing date of Aug. 1, 2012, U.S. Provisional PatentApplication Ser. No. 61/703,331 having a filing date of Sep. 20, 2012,U.S. Provisional Patent Application Ser. No. 61/707,320 having a filingdate of Sep. 28, 2012, and U.S. Provisional Patent Application Ser. No.61/717,946 having a filing date of Oct. 24, 2012, all of which areincorporated herein in their entirety by reference.

BACKGROUND OF THE INVENTION

Blow molding has been utilized for a number of years to form a varietyof hollow plastic parts. It has proven effective to form single layer aswell as multi-layer materials and, with more recent advances, has beenused to form a variety of complex shapes, for instance via 3D blowmolding techniques. The versatility of blow molding processes isproviding a route to the formation of multi-functional, one-piece blowmolded components that can reduce weight and simplify assembly ofconsumer goods as well as manufacturing and production devices.

Many of the applications that could benefit from the utilization of blowmolded components are quite demanding, and require components that canwithstand a variety of both chemical and mechanical insults. Forexample, components for use in transport and transportation applicationsshould be able to provide a long life under operating conditions thatinclude temperature fluctuations as well as movement during use. Thus,materials generally require both strength and flexibility. Moreover,materials should be resistant to and impermeable to fluids that may beencountered during use such as oil, gas, coolants, water, air, etc. thatmay also be heated or cooled during use.

Polymeric materials that can be blow molded to form products thatexhibit flexibility in addition to high strength and resistanceproperties are of significant commercial interest. Such materials havebeen formed in the past by uniformly mixing an elastomeric componentwith a thermoplastic polyolefin such that the elastomer is intimatelyand uniformly dispersed as a discrete or co-continuous phase within acontinuous phase of the polyolefin. Vulcanization of the compositecrosslinks the components and provides improved temperature and chemicalresistance to the composition. When vulcanization is carried out duringcombination of the various polymeric components it is termed dynamicvulcanization.

Polyarylene sulfides are high-performance polymers that may withstandhigh thermal, chemical, and mechanical stresses and are beneficiallyutilized in a wide variety of applications. Polyarylene sulfides haveoften been blended with other polymers to improve characteristics of theproduct composition. For example, elastomeric impact modifiers have beenfound beneficial for improvement of the physical properties ofthermoplastic compositions. Compositions including blends of polyarylenesulfides with impact modifying polymers have been considered for highperformance, high temperature applications.

Unfortunately, elastomeric polymers generally considered useful forimpact modification are not compatible with polyarylene sulfides andphase separation has been a problem in forming compositions of the two.Attempts have been made to improve the composition formation, forinstance through the utilization of compatibilizers. However, even uponsuch modifications, compositions including polyarylene sulfides incombination with impact modifying polymers still fail to provide productperformance as desired, particularly in applications that require bothhigh heat resistance and high impact resistance.

What are needed in the art are thermoplastic compositions that areamenable to blow molding formation methods and that also exhibit highstrength characteristics as well as resistance to degradation, even inextreme environments. More specifically, what are needed are blow moldedcomponents that can withstand utilization in harsh working environments.

SUMMARY OF THE INVENTION

Disclosed in one embodiment is a component that includes a blow moldedthermoplastic composition. The thermoplastic composition includes apolyarylene sulfide and a crosslinked impact modifier. The compositionhas excellent material characteristics. For example, the composition canhave a notched Charpy impact strength of greater than about 3 kJ/m² asdetermined according to ISO Test No. 197-1 at 23° C. and a tensilemodulus of less than about 3000 MPa as determined according to ISO TestNo. 527 at a temperature of 23° C. and a test speed of 5 mm/min.

Also disclosed is a method for forming a component. The method caninclude blow molding a thermoplastic composition that includes apolyarylene sulfide and a crosslinked impact modifier.

Components as may be formed can include components for use in harshenvironments, such as in transportation applications (e.g., automotivecomponents) or transport applications (e.g., oil and gas fieldcomponents). By way of example, transport components can include flowlines for use in oil and gas fields. Automotive components can includefuel system components such as gas tanks, and fuel filler necks;interior HVAC components including both reservoirs and ducting; interiorand exterior components such as running boards, grill guards, etc.; andengine components such as single layer and multi-layer hoses.

BRIEF DESCRIPTION OF THE FIGURES

The present disclosure may be better understood with reference to thefollowing figures:

FIG. 1 illustrates a step in a blow molding process as may be utilizedin forming a component from the thermoplastic composition.

FIG. 2 illustrates a step in a blow molding process as may be utilizedin forming a component from the thermoplastic composition.

FIG. 3 illustrates a step in a blow molding process as may be utilizedin forming a component from the thermoplastic composition.

FIG. 4 illustrates a step in a blow molding process as may be utilizedin forming a component from the thermoplastic composition.

FIG. 5 illustrates a step in a blow molding process as may be utilizedin forming a component from the thermoplastic composition.

FIG. 6 illustrates a continuous blow molding process as may be utilizedin forming a tubular component from the thermoplastic composition

FIG. 7 is a schematic representation of an oil and gas field that mayinclude components as described herein.

FIG. 8 is a schematic representation of a multilayer riser including oneor more blow molded layers formed from the thermoplastic composition.

FIG. 9 is a schematic representation of an automobile body showing somerepresentative examples of automotive components that may include a blowmolded thermoplastic composition.

FIG. 10 is a schematic representation of a fuel tank filler neck thatmay include the blow molded thermoplastic composition.

FIG. 11 is a schematic representation of a fluid reservoir such as a gastank that may include the blow molded thermoplastic composition.

FIG. 12 is a schematic representation of an air duct that may includethe blow molded thermoplastic composition.

FIG. 13 is a schematic representation of another air duct that mayinclude the blow molded thermoplastic composition.

FIG. 14 is a schematic representation of a running board that mayinclude the blow molded thermoplastic composition.

FIG. 15 is a schematic representation of a support structure that mayinclude the blow molded thermoplastic composition.

FIG. 16 is a single layer tubular member as may be formed from thethermoplastic composition.

FIG. 17 is a multi-layer tubular member, one or more layers of which maybe formed from the thermoplastic composition.

FIG. 18 is a schematic representation of a process for forming thethermoplastic composition.

FIG. 19 illustrates the sample used in determination of melt strengthand melt elongation of thermoplastic compositions described herein.

FIG. 20 illustrates the effect of temperature change on the notchedCharpy impact strength of a thermoplastic composition as describedherein and that of a comparison composition.

FIG. 21A is a scanning electron microscope image of a comparisonthermoplastic composition, and FIG. 21B is a scanning electronmicroscope image of a thermoplastic composition as described herein.

FIG. 22 compares the effect of sulfuric acid exposure on strengthcharacteristics of thermoplastic compositions as described herein and acomparison composition.

FIG. 23 provides the log of the complex viscosity obtained forthermoplastic compositions described herein as a function of the shearrate.

FIG. 24 provides the melt strength of thermoplastic compositionsdescribed herein as a function of the Hencky strain.

FIG. 25 provides the melt elongation for thermoplastic compositionsdescribed herein as a function of Hencky strain.

FIG. 26 illustrates a blow molded container formed of the thermoplasticcomposition.

FIG. 27A and FIG. 27B are cross sectional images of the container shownin FIG. 26.

FIG. 28 illustrates the daily weight loss for testing samples indetermination of permeation resistance of thermoplastic compositions toCE10 fuel blend.

FIG. 29 illustrates the daily weight loss for testing samples indetermination of permeation resistance of thermoplastic compositions toCM15A fuel blend.

FIG. 30 illustrates the daily weight loss for testing samples indetermination of permeation resistance of thermoplastic compositions tomethanol.

DETAILED DESCRIPTION

It is to be understood by one of ordinary skill in the art that thepresent discussion is a description of exemplary embodiments only, andis not intended as limiting the broader aspects of the presentdisclosure.

The present disclosure is generally directed to components that includea blow molded thermoplastic composition that exhibits excellent strengthand flexibility characteristics as well as resistance to chemicaldegradation due to contact with, e.g., water, oil, gasoline, gases,synthetic or natural chemicals, etc. Beneficially, the thermoplasticcomposition can maintain good physical characteristics even whenutilized in extreme environments such as may be encountered intransportation and transport applications. For example, thethermoplastic composition can maintain good physical characteristicsunder conditions in which the components are subjected to motive forces.

The thermoplastic composition can be formed according to a meltprocessing technique that includes combining a polyarylene sulfide withan impact modifier to form a mixture and subjecting the mixture todynamic vulcanization. More specifically, the polyarylene sulfide can becombined with the impact modifier and this mixture can be subjected toshear conditions such that the impact modifier becomes well distributedthroughout the polyarylene sulfide. Following formation of the mixture,a polyfunctional crosslinking agent can be added. The polyfunctionalcrosslinking agent can react with the components of the mixture to formcrosslinks in the composition, for instance within and between thepolymer chains of the impact modifier.

Without being bound to any particular theory, it is believed that byadding the polyfunctional crosslinking agent following distribution ofthe impact modifier throughout the polyarylene sulfide, interactionbetween the polyarylene sulfide, the impact modifier, and thecrosslinking agent within the melt processing unit can be improved,leading to improved distribution of the crosslinked impact modifierthroughout the composition. The improved distribution of the crosslinkedimpact modifier throughout the composition can improve the strength andflexibility characteristics of the composition, e.g., the ability of thecomposition to maintain strength under deformation, as well as provide acomposition with good processibility that can be utilized to form a blowmolded product that can exhibit excellent resistance to degradationunder a variety of conditions.

The high strength and flexibility characteristics of the thermoplasticcomposition can be evident by examination of the tensile, flexural,and/or impact properties of the materials. For example, thethermoplastic composition can have a notched Charpy impact strength ofgreater than about 3 kJ/m², greater than about 3.5 kJ/m², greater thanabout 5 kJ/m², greater than about 10 kJ/m², greater than about 15 kJ/m²,greater than about 30 kJ/m², greater than about 33 kJ/m², greater thanabout 40 kJ/m², greater than about 45 kJ/m², or greater than about 50kJ/m² as determined according to ISO Test No. 179-1 (technicallyequivalent to ASTM D256, Method B) at 23° C. The unnotched Charpysamples do not break under testing conditions of ISO Test No. 180 at 23°C. (technically equivalent to ASTM D256).

Beneficially, the thermoplastic composition can maintain good physicalcharacteristics even at extreme temperatures, including both high andlow temperatures. For instance, the thermoplastic composition can have anotched Charpy impact strength of greater than about 8 kJ/m², greaterthan about 9 kJ/m², greater than about 10 kJ/m², greater than about 14kJ/m², greater than about 15 kJ/m², greater than about 18 kJ/m², orgreater than about 20 kJ/m² as determined according to ISO Test No.179-1 at −30° C.; and can have a notched Charpy impact strength ofgreater than about 8 kJ/m², greater than about 9 kJ/m², greater thanabout 10 kJ/m², greater than about 11 kJ/m², greater than about 12kJ/m², or greater than about 15 kJ/m² as determined according to ISOTest No. 179-1 at −40° C.

Moreover, the effect of temperature change on the thermoplasticcomposition can be surprisingly small. For instance, the ratio of thenotched Charpy impact strength as determined according to ISO Test No.179-1 at 23° C. to that at −30° C. can be greater than about 3.5,greater than about 3.6, or greater than about 3.7. Thus, and asdescribed in more detail in the example section below, as thetemperature increases the impact strength of the thermoplasticcomposition also increases, as expected, but the rate of increase of theimpact strength is very high, particularly as compared to a compositionthat does not include the dynamically crosslinked impact modifier.Accordingly, the thermoplastic composition can exhibit excellentstrength characteristics at a wide range of temperatures.

The thermoplastic composition can exhibit very good tensilecharacteristics. For example, the thermoplastic composition can have atensile elongation at yield of greater than about 4.5%, greater thanabout 6%, greater than about 7%, greater than about 10%, greater thanabout 25%, greater than about 35%, greater than about 50%, greater thanabout 70%, greater than about 75%, greater than about 80%, or greaterthan about 90%. Similarly, the tensile elongation at break can be quitehigh, for instance greater than about 10%, greater than about 25%,greater than about 35%, greater than about 50%, greater than about 70%,greater than about 75%, greater than about 80%, or greater than about90%. The strain at break can be greater than about 5%, greater thanabout 15%, greater than about 20%, or greater than about 25%. Forinstance the strain at break can be about 90%. The yield strain canlikewise be high, for instance greater than about 5%, greater than about15%, greater than about 20%, or greater than about 25%. The yield stresscan be, for example, greater than about 50% or greater than about 53%.The thermoplastic composition may have a tensile strength at break ofgreater than about 30 MPa, greater than about 35 MPa, greater than about40 MPa, greater than about 45 MPa, or greater than about 70 MPa.

In addition, the thermoplastic composition can have a relatively lowtensile modulus. For instance, the thermoplastic composition can have atensile modulus less than about 3000 MPa, less than about 2300 MPa, lessthan about 2000 MPa, less than about 1500 MPa, or less than about 1100MPa as determined according to ISO Test No. 527 at a temperature of 23°C. and a test speed of 5 mm/min.

The thermoplastic composition can exhibit good characteristics afterannealing as well. For instance, following annealing at a temperature ofabout 230° C. for a period of time of about 2 hours, the tensile modulusof the composition can be less than about 2500 MPa, less than about 2300MPa, or less than about 2250 MPa. The tensile strength at break afterannealing can be greater than about 50 MPa, or greater than about 55MPa, as measured according to ISO Test No. 527 at a temperature of 23°C. and a test speed of 5 mm/min.

The thermoplastic composition can also be utilized continuously at hightemperature, for instance at a continuous use temperature of up to about150° C., about 160° C., or about 165° C. without loss of tensilestrength. For example, the thermoplastic composition can maintaingreater than about 95%, for instance about 100% of the original tensilestrength after 1000 hours of heat aging at 165° C. and can maintaingreater than about 95%, for instance about 100% of the original tensileelongation at yield after 1000 hours heat aging at 135° C.

Tensile characteristics can be determined according to ISO Test No. 527at a temperature of 23° C. and a test speed of 5 mm/min or 50 mm/min(technically equivalent to ASTM D623 at 23° C.).

The flexural characteristics of the composition can be determinedaccording to ISO Test No. 178 (technically equivalent to ASTM D790 at atemperature of 23° C. and a testing speed of 2 mm/min. For example, theflexural modulus of the composition can be less than about 2500 MPa,less than about 2300 MPa, less than about 2000 MPa, less than about 1800MPa, or less than about 1500 MPa. The thermoplastic composition may havea flexural strength at break of greater than about 30 MPa, greater thanabout 35 MPa, greater than about 40 MPa, greater than about 45 MPa, orgreater than about 70 MPa.

The deflection temperature under load of the thermoplastic compositioncan be relatively high. For example, the deflection temperature underload of the thermoplastic composition can be greater than about 80° C.,greater than about 90° C., greater than about 100° C., or greater thanabout 105° C., as determined according to ISO Test No. 75-2 (technicallyequivalent to ASTM D790) at 1.8 MPa.

The Vicat softening point can be greater than about 200° C. or greaterthan about 250° C., for instance about 270° C. as determined accordingto the Vicat A test when a load of 10 N is used at a heating rate of 50K/hr. For the Vicat B test, when a load of 50 N is used at a heatingrate of 50 K/hr, the Vicat softening point can be greater than about100° C., greater than about 150° C. greater than about 175° C., orgreater than about 190° C., for instance about 200° C. The Vicatsoftening point can be determined according to ISO Test No. 306(technically equivalent to ASTM D1525).

The thermoplastic composition can also exhibit excellent stabilityduring long term exposure to harsh environmental conditions. Forinstance, under long term exposure to an acidic environment, thethermoplastic composition can exhibit little loss in strengthcharacteristics. For instance, following 500 hours exposure to a strongacid (e.g., a solution of about 5% or more strong acid such as sulfuricacid, hydrochloric acid, nitric acid, perchloric acid, etc.), thethermoplastic composition can exhibit a loss in Charpy notched impactstrength of less than about 17%, or less than about 16% followingexposure of about 500 hours to a strong acid solution at a temperatureof about 40° C., and can exhibit a loss in Charpy notched impactstrength of less than about 25%, or less than about 22% followingexposure of about 500 hours to a strong acid solution at a temperatureof about 80° C. Even under harsher conditions, for instance in a 10%sulfuric acid solution held at a temperature of about 80° C. for 1000hours, the thermoplastic composition can maintain about 80% or more ofthe initial Charpy notched impact strength. The thermoplasticcomposition can also maintain desirable strength characteristicsfollowing exposure to other potentially degrading materials, such assalts, e.g., road salts as may be encountered in automotiveapplications.

Permeation resistance can be important for a wide variety ofapplications for the thermoplastic composition, for instance whenutilizing the composition in formation of blow molded storage tanks orthe like. The composition can exhibit excellent permeation resistance toa wide variety of materials. For instance, a blow molded product formedof the composition can exhibit a permeation resistance to a fuel or afuel source (e.g., gasoline, diesel fuel, jet fuel, unrefined or refinedoil, etc.) of less than about 10 g-mm/m²-day, less than about 5g-mm/m²-day, less than about 3 g-mm/m²-day, or less than about 2g-mm/m²-day. By way of example, the thermoplastic composition (or a blowmolded product formed of the thermoplastic composition) can exhibit apermeation resistance to an ethanol blend of ethanol/iso-octane/tolueneat a weight ratio of 10:45:45 at 40° C. of less than about 10g-mm/m²-day, less than about 3 g-mm/m²-day, less than about 2.5g-mm/m²-day, less than about 1 g-mm/m²-day, or less than about 0.1g-mm/m²-day. The permeation resistance to a blend of 15 wt. % methanoland 85 wt. % oxygenated fuel (CM15A) at 40° C. can be less than about 5g-mm/m²-day, less than about 3 g-mm/m²-day, less than about 2.5g-mm/m²-day, less than about 1 g-mm/m²-day, less than about 0.5g-mm/m²-day, less than about 0.3 g-mm/m²-day, or less than about 0.15g-mm/m²-day. The permeation resistance to methanol at 40° C. can be lessthan about 1 g-mm/m²-day, less than about 0.5 g-mm/m²-day, less thanabout 0.25 g-mm/m²-day, less than about 0.1 g-mm/m²-day, or less thanabout 0.06 g-mm/m²-day. Permeation resistance can be determinedaccording to SAE Testing Method No. J2665. In addition, thethermoplastic composition can maintain the original density followinglong term exposure to hydrocarbons. For example, the composition canmaintain greater than about 95% of original density, greater than about96% of original density, such as about 99% of original density followinglong term (e.g., greater than about 14 days) exposure to hydrocarbonssuch as heptane, cyclohexane, toluene, and so forth, or combinations ofhydrocarbons.

The thermoplastic composition can exhibit good heat resistance and flameretardant characteristics. For instance, the composition can meet theV-0 flammability standard at a thickness of 0.2 millimeters. The flameretarding efficacy may be determined according to the UL 94 VerticalBurn Test procedure of the “Test for Flammability of Plastic Materialsfor Parts in Devices and Appliances”, 5th Edition, Oct. 29, 1996. Theratings according to the UL 94 test are listed in the following table:

Rating Afterflame Time (s) Burning Drips Burn to Clamp V-0 <10 No No V-1<30 No No V-2 <30 Yes No Fail <30 Yes Fail >30 No

The “afterflame time” is an average value determined by dividing thetotal afterflame time (an aggregate value of all samples tested) by thenumber of samples. The total afterflame time is the sum of the time (inseconds) that all the samples remained ignited after two separateapplications of a flame as described in the UL-94 VTM test. Shorter timeperiods indicate better flame resistance, i.e., the flame went outfaster. For a V-0 rating, the total afterflame time for five (5)samples, each having two applications of flame, must not exceed 50seconds. Using the flame retardant of the present invention, articlesmay achieve at least a V-1 rating, and typically a V-0 rating, forspecimens having a thickness of 0.2 millimeters.

The thermoplastic composition can also exhibit good processingcharacteristics, for instance as demonstrated by the melt viscosity ofthe composition. For instance, the thermoplastic composition can have amelt viscosity of less than about 2800 poise as measured on a capillaryrheometer at 316° C. and 400 sec⁻¹ with the viscosity measurement takenafter five minutes of constant shear. Moreover, the thermoplasticcomposition can exhibit improved melt stability over time as compared tothermoplastic compositions that do not include crosslinked impactmodifiers. Thermoplastic compositions containing a polyarylene sulfidethat do not include a crosslinked impact modifier tend to exhibit anincrease in melt viscosity over time, while disclosed compositions canmaintain or even decrease in melt viscosity over time.

The thermoplastic composition can have a complex viscosity as determinedat low shear (0.1 radians per second (rad/s)) and 310° C. of greaterthan about 10 kPa/sec, greater than about 25 kPa/sec, greater than about40 kPa/sec, greater than about 50 kPa/sec, greater than about 75kPa/sec, greater than about 200 kPa/sec, greater than about 250 kPa/sec,greater than about 300 kPa/sec, greater than about 350 kPa/sec, greaterthan about 400 kPa/sec, or greater than about 450 kPa/sec. Higher valuefor complex viscosity at low shear is indicative of the crosslinkedstructure of the composition and the higher melt strength of thethermoplastic composition. In addition, the thermoplastic compositioncan exhibit high shear sensitivity, which indicates excellentcharacteristics for use in blow molding formation processes.

The thermoplastic composition can be processed according to a blowmolding process in formation of an automotive component. Blow moldingprocesses such as continuous and intermittent extrusion blow molding,injection blow molding, and stretch blow molding can be utilized. 3Dblow molding, dual process overmolding, and so forth are likewiseencompassed herein.

One blow molding process is illustrated sequentially in FIGS. 1 through5. Referring to FIG. 1, for instance, the thermoplastic composition isfirst heated and extruded into a parison 20 using a die 22 attached toan extrusion device. As shown, the parison 20 is extruded into adownward direction. When the parison 20 is formed as shown in FIG. 1,the composition should have sufficient melt strength to prevent gravityfrom undesirably elongating portions of the parison and thereby formingnon-uniform wall thicknesses and other imperfections. On the other hand,the melt elongation must also be sufficiently high to allow forprocessibility of the composition. Thus, there must be a balance betweenmelt strength and melt elongation such that the composition can beprocessed while maintaining uniform wall thickness. In other words, theengineering stress must be sufficiently high at a high percent strain toallow for processibility of the composition.

As shown in FIG. 1, the parison 20 is extruded adjacent a clampingmechanism 24 which is typically attached to a robotic arm. Alsopositioned to receive the parison 20 is a molding device 26. In theembodiment illustrated, the molding device 26 includes a first portion28 and a second portion 30 that together combine to form athree-dimensional mold cavity 32. In the embodiment illustrated bothportions 28 and 30 of the molding device move toward and away from eachother. In an alternative embodiment, however, one portion may remainstationary while only the other portion moves. A molding device may alsoinclude more than two portions, as is known.

Referring to FIG. 2, the next step in the process is for the clampingmechanism 24 to engage a top of the parison 20 after the parison 20 hasreached a desired length. As shown in FIG. 3, the clamping mechanismthen moves the parison into a position so that the parison can interactwith the molding device 26. The clamping mechanism 24 can be moved withthe aid of a robotic arm.

As can be appreciated, a certain period of time elapses from formationof the parison 20 to clamping and moving the parison 20 into engagementwith the molding device 26. During this stage of the process, the meltstrength of the polymeric composition should be high enough such thatthe parison 20 maintains its shape during movement. The polymericcomposition should also be capable of remaining in a semi-fluid stateand not solidifying too rapidly before blow molding commences.

As shown in FIG. 3, the robotic arm also engages the bottom of theparison 20 with a fluid supply device 34 which is used during blowmolding.

Referring to FIG. 4, once the parison 20 has been moved into position,the first portion 28 and the second portion 30 of the molding device 26move together such that the parison 20 partially extends through themold cavity 32 as shown in FIG. 4.

As shown in FIG. 4, the first portion 28 includes a top section 40 andthe second portion 30 includes a top section 42. In the embodimentillustrated, the bottom sections of the molding device 26 first closeleaving the top sections 40 and 42 open. In this manner, the parison 20can first engage the bottom portion of the molding cavity 32. Theclamping device 24 can then robotically move the top of the parisonprior to closing the top sections 40 and 42 of the molding device. Oncethe clamping mechanism is properly located, as shown in FIG. 5, the topsections of the mold close such that the parison extends the entirelength of the mold cavity.

Having separately movable top sections as shown in FIGS. 4 and 5 areneeded in some molding applications when complex shapes are beingformed. Having separate sections of the mold surround the parison atdifferent times allows a robotic arm to continue to manipulate theparison in order to place in the resulting part angular displacements.

Once the top sections 40 and 42 of the molding device 26 are closed asshown in FIG. 5, a gas, such as an inert gas, is fed into the parsion 20from the gas supply 34. The gas supplies sufficient pressure against theinterior surface of the parison such that the parison conforms to theshape of the mold cavity 32.

After blow molding, the finished component is then removed and used asdesired. In one embodiment, cool air can be injected into the moldedpart for solidifying the polymer prior to removal from the moldingdevice 26.

Blow molding processes are not limited to robotic 3-D blow moldingmethodology as illustrated in FIGS. 1-5, however, and other blow moldingprocesses may alternatively be utilized in forming a component. By wayof example, in one embodiment, a continuous blow molding process can beused to form larger items, such as long tubular components as may beuseful in piping applications. FIG. 6 presents a schematic illustrationof one method as may be utilized in forming a long tubular componentaccording to a continuous blow molding process. In a continuous process,a stationary extruder (not shown) can plasticize the force the moltenthermoplastic composition through a head to form a continuous parison601. An accumulator 605 can be used to support the parison and preventsagging prior to molding. The parison may be fed to a mold formed ofarticulated sections 602, 603 that travel in conjunction with thecontinuous parison on a mold conveyor assembly 604. Air under pressureis applied to the parison to blow mold the thermoplastic compositionwithin the mold. After the thermoplastic composition has been molded andsufficiently cooled within the mold as the mold and thermoplasticcomposition travel together, the mold segments are separated from oneanother and the formed section of the component (e.g., the pipe) 606 isremoved from the conveyor and taken up, as on a take-up reel (notshown).

A component can include the thermoplastic composition throughout theentire component or only a portion of the component. For instance, whenconsidering a component having a large aspect ratio (L/D>1), such as atubular member, the component can be formed such that the thermoplasticcomposition extends along a section of the component and an adjacentsection can be formed of a different composition, for instance adifferent thermoplastic composition. Such a component can be formed by,e.g., altering the material that is fed to a blow molding device duringa formation process. The component can include an area in which the twomaterials are mixed that represents a border region between a firstsection and a second section formed of different materials. A componentcan include a single section formed of the thermoplastic composition ora plurality of sections, as desired. Moreover, other sections of acomponent can be formed of multiple different materials. By way ofexample, when considering a tubular component such as a fluid conduit,both ends of the tubular component can be formed of the thermoplasticcomposition and a center section can be formed of a less flexiblecomposition. Thus, the more flexible ends can be utilized to tightlyaffix the component to other components of a system. Alternatively, acenter section of a component could be formed from the thermoplasticcomposition, which can improve flexibility of the component in thatsection, making installation of the component easier.

A large variety of components can be formed according to a process thatincludes blow molding the thermoplastic composition. In one embodiment,components as may be formed may be used in transport application, forinstance in transport of oil and gas applications. In one particularembodiment, the thermoplastic composition can be utilized in forming aflowline for use in transporting oil and/or gas at or from a productionfacility. By way of example, the thermoplastic composition may be blowmolded to form a single layer flowline or one or more layers of a bondedor unbounded flowline, such as a multilayer riser or pipeline or acoupling or connector that can be utilized in attaching flowlinesegments to one another.

FIG. 7 illustrates a typical offshore field that can incorporate aplurality of different types of flowlines, one or more of which mayinclude at least one layer formed of the blow molded thermoplasticcomposition, for instance as a barrier layer. As can be seen, theoffshore field can include fixed risers 791 that can carry productionfluid from the sea floor 792 to a platform 795. The thermoplasticcomposition can be utilized in forming other types of risers as wellsuch as flexible risers that can convey production fluid from a subseapipeline end manifold through a catenary moored buoy and a yoke to afloating vessel, as is known. Such flexible risers can have anyconfiguration such as a steep S, a lazy S, a steep wave, or a lazy waveconfiguration.

The field can include infield flowlines 793 that can include the blowmolded thermoplastic composition and can carry production fluid,supporting fluids, umbilicals, etc., within the field. The system alsoincludes a plurality of tie-ins 794 at which point different flowlinescan be merged, for instance to form a bundled riser and/or whereindividual flowlines may be altered, for instance through expansion. Thesystem also includes a plurality of satellite wells and manifolds 798from which the hydrocarbon production fluid is obtained. An exportpipeline 797 can carry production fluid from the platform 795 to shore,a storage facility, or a transport vessel. The export pipeline 797 mayalso include one or more crossings 796 to by-pass other flowlines, e.g.,another pipeline 799. Though illustrated as an offshore facility, itshould be understood that oil and gas facilities in any location canutilized blow molded components as described herein, and the disclosureis not limited to offshore facilities.

Referring to FIG. 8, one embodiment of a flexible riser 800 that canincorporate one or more layers formed of the blow molded thermoplasticcomposition is shown. As shown, the riser 800 has several concentriclayers. An innermost layer is generally termed the carcass 802 and canbe formed of helically wound stainless steel strip so as to provideresistance against external pressures. The carcass 802 is generally ametal (e.g., stainless steel) tube that supports the adjacent barrierlayer 806 and prevents riser collapse due to pressure or loads appliedduring operation. The bore of the flexible riser 800 can vary dependingupon the fluid to be carried by the riser. For instance, the riser 800can have a smooth bore when intended for use to carry a supporting fluidsuch as an injection fluid (e.g., water and/or methanol) and can have arough bore when utilized to carry production fluids (e.g., oil and gas).The carcass 802, when present, can generally be between about 5 andabout 10 millimeters in thickness. According to one embodiment, thecarcass can be formed by helically wound stainless steel strips thatinterlock with one another to form the strong, interconnected carcass.

The barrier layer 806 is immediately adjacent the carcass 802. Thebarrier layer is formed of the blow molded thermoplastic composition andprovides strength and flexibility as well as resistance to chemicalassaults while preventing permeation of the fluid carried by the riserthrough the riser wall. The barrier layer 806 can generally be betweenabout 3 and about 10 millimeters in thickness and can be extruded from amelt over the carcass 2.

The riser 8 can also include an outer layer 822 that provides anexternal sleeve and an external fluid barrier as well as providingprotection to the riser from external damage due to, e.g., abrasion orencounters with environmental materials. The outer layer 822 can beformed of a polymeric material such as the thermoplastic composition ora high density polyethylene that can resist both mechanical damage andintrusion of seawater to the inner layers of the riser. According to oneembodiment, the outer layer 822 can be a composite material thatincludes a polymeric material in conjunction with a reinforcementmaterial such as carbon fibers, carbon steel fibers, or glass fibers.

A hoop strength layer 804 can be located external to the barrier layer806 to increase the ability of the riser to withstand hoop stressescaused by forced applied to the riser wall by a pressure differential.The hoop strength layer can generally be a metal layer formed of, e.g.,a helically wound strip of carbon steel that can form a layer of fromabout 3 to about 7 millimeters in thickness. Additional strength layers818 and 820 can be formed of helically-wound metal (generally carbonsteel) strips. The strength layers 818 and 820 can be separated from thehoop strength layer 804 and from each other by polymeric anti-wearlayers 817 and 819. Though the riser 800 includes two strength layers818, 820, it should be understood that a riser may include any suitablenumber of strength layers, including no strength layers, one, two,three, or more strength layers. The strength layers 818, 820 may have awidth of from about 1 millimeter to about 5 millimeters.

The intervening anti-wear layers 817, 819 can be formed of thethermplastic composition or alternatively can be formed of otherpolymers such as a polyamide, a high density polyethylene, or the like.In one embodiment, the anti-wear layers 817, 819 can be a compositematerial that includes unidirectional fibers, for instance carbon orglass fibers. The anti-wear layers 817, 819 can prevent wear of theadjacent strength layers that can come about due to motion of the stripsforming the layers. The anti-wear layers 817, 819 can also preventbirdcaging of the adjacent layers. As with the strength layers 818, 820of the riser 800, the number of anti-wear layers is not particularlylimited, and a riser can include no anti-wear layers, one anti-wearlayers, or multiple anti-wear layers depending upon the depth and localenvironment in which the riser will be utilized, the fluid to be carriedby the riser, and so forth. The anti-wear layers 817, 819, can berelatively thin, for instance between about 0.2 and about 1.5millimeters.

While the above description is for an unbounded flexible riser, itshould be understood that the thermoplastic composition may likewise beutilized in forming a bonded flowline. For example, the thermoplasticcomposition may be directly blow molded on to an adjacent layer of acontinuous tubular member to form a bonded flowline for use in anoffshore oil and gas facility.

In another embodiment, the thermoplastic composition may be blow moldedto form a component for use in the transportation field. For instance,blow molded components of the thermoplastic composition can be utilizedin forming automotive components. By way of example and withoutlimitation, automotive components of the fuel system, the HVAC system,the engine cooling system, as well as interior and exterior portions ofthe vehicle body can be formed according to a process that includes blowmolding the thermoplastic composition. FIG. 9 illustrates a car body 50including several automotive components as may include the blow moldedthermoplastic composition such as struts 52, supports 54 (e.g., radiatorsupports), grill guard 56, the floor pan 58, the trunk flooring 59, theinner pillars 53, and so forth.

In one embodiment, components of the fuel system such as the fuel fillerneck can be formed of the thermoplastic composition. FIG. 10 illustratesa fuel filler neck 60 as may be blow molded from the thermoplasticcomposition. A filler tube 64 and a gas cap 66 can be associated withthe filler neck 60. The filler neck 60 generally includes a one-piece,seamless funnel member having a generally tubular body, as shown. Thefiller neck 60 may be adapted to receive a nozzle receptor, which is aninsert for receiving a fuel nozzle during fueling. The filler neckincludes at one end an opening adapted to receive the gas cap 66, whichin this embodiment screws directly into threads 67 integrally formed inthe filler neck 60. The threads 67 may be screw, quarter-turn,eighth-turn or quick-turn configurations, or any other known threadconfiguration. The filler neck 60 narrows as shown at 69 from the firstend to an opposite end that includes an outlet opening 62, which iscoupled to a first end 61 of the filler tube 64 via a joint 63. The gascap 66, which can seat against a rolled-over sealing surface 65 formedabout the inlet opening, may include a seal 68 to prevent fuel or vaporloss between the gas cap 66 and the filler neck 60. The one-piece,seamless filler neck 60 may be formed from the thermoplastic compositionaccording to a blow molding process. The a flow line such as the fillertube 64 may alternatively or additionally be formed from thethermoplastic composition in a blow molding process, as discussedfurther herein.

Automotive components as may include the blow molded thermoplasticcomposition can include reservoirs and tanks. For example, FIG. 11illustrates a fuel tank 70 that can be formed according to a blowmolding process. The fuel tank 70 can have a relatively complicatedshape, and can include various features such as a pump unit mountinghole 74 formed in an upper surface of the tank for ingress and egress ofa fuel pump (not shown) into and from the fuel tank 70. In addition, afuel inlet hole 75 into which fuel is supplied from an inlet pipe as maybe connected to a fuel filler neck 60 as illustrated in FIG. 10 can beformed in a side surface or the upper surface of the fuel tank 70.

The fuel tank 70 can include an outer circumferential rib 72 formedaround a full circumference of the fuel tank 70, and mounting holes 73can be formed in the outer circumferential rib 72 in severalpredetermined locations such as in corners thereof. The mounting holes73 can be used to fasten the fuel tank 70 to the vehicle body withbolts. The fuel tank 70 can also include a mounting hole 76 on the upperside of the fuel tank 70 that can be connectable to a hose (not shown)for collecting evaporated fuel in an interior of the fuel tank 70. Thehose can be a single layer or multilayer hose, for instance such asdescribed in more detail within, and can include the thermoplasticcomposition in one or more layers of the hose.

The fuel tank 70 can be a single layer or multi-layer fuel tank. Forinstance, an outer wall of the fuel tank 70 can be formed through blowmolding and can include one or more layers such as, without limitation,a skin layer, an exterior main layer, an exterior adhesive layer, abarrier layer, an interior adhesive layer and an interior main layer inthat order from an outside thereof. The thermoplastic composition canform one or more layers of the multi-layer fuel tank 70. For instance,as the thermoplastic composition can be highly impermeable, thethermoplastic composition can be blow molded to form at least thebarrier layer of a multi-layer fuel tank. Other reservoirs as may beformed from the thermoplastic composition can include, withoutlimitation, reservoirs for the windshield washing fluid, the expansiontank, and so forth.

Another automotive system that may beneficially take advantage of theblow molding capabilities of the thermoplastic composition is theventilation system. By way of example, FIG. 12 illustrates a tubular airduct 80 that may be formed from the thermoplastic composition accordingto a blow molding process, for instance an injection blow moldingprocess. As can be seen, the air duct 80 has an elongated body portion82 with integrally formed, flanged first and second ends 84 and 86,respectively. The air duct 80 also includes a laterally extending port88. The laterally extending port 88 can be included on the tubular bodyto allow air to be directed to and from multiple devices on the vehicle.For example, the air duct 80 can be utilized in an exhaust gasrecirculation system according to known practice to reduce the exhaustemissions of the engine. The air duct 80 may be utilized to transportclean air from a filter to multiple components of the vehicle such asthe inlet manifold as well as to the heating and ventilating system inthe passenger compartment, and the laterally extending port 88 can beutilized to divert a portion of the air in the duct 80 to a secondarycomponent.

The air duct 80 can also include a flexible portion 83 that may beformed between the port 88 and end 84 or 86 to facilitate flexibilityand installation of the air duct 80. The flanged ends 84 and 86 canpermit the air duct 80 to be secured in an air induction system by useof conventional hose clamps in a well-known manner. The air duct 80 is ablow molded component, and can include parting, or split, lines 85 and87 that are substantially diametrically opposite each other and alsodisplaced approximately ninety degrees from the port 88.

FIG. 13 illustrates another example of an air duct 90 as may include theblow molded thermoplastic composition. In this embodiment, the air ductmay be quite large and may be a portion of a cross car beam 90. Thestrength characteristics of the thermoplastic composition can bebeneficial when forming a large air duct 90 as illustrated. Cross carbeam 90 includes a U-shaped rigid support 92 having a plurality ofperforations (not shown), and a blow molded rigid, continuous andunitary air duct 95 of the thermoplastic composition, having a hollowinterior 97. Rigid hollow duct 95 is attached to rigid support 92 bymeans of a plurality of attachment heads 94. Duct 95 has extensions 98,91, 93 and 96 that each provide gaseous communication with the interior97 of duct 95. For example, conditioned air (e.g., heated, cooled ordehumidified air) introduced through extension 91 travels throughinterior 97 and can exit duct 95 through extensions 98, 93 and 96. Crosscar beam 90 can be used as a cross car beam extending between the doorpillars of a vehicle, such as a car or truck.

Exterior components of a vehicle can also be formed from thethermoplastic composition by use of a blow molding method. For instance,FIG. 14 illustrates a running board assembly 100 as may include the blowmolded thermoplastic composition. The running board assembly 100includes a running board 102, a step pad 104 and a trim strip 106. Therunning board 100 has an upper support surface 103. The step pad 104 canbe adhered to the supporting surface 103. The running board 102 may beformed of the thermoplastic composition in a blow molding procedure. Therunning board can include a plurality of recesses as shown that may beformed during the blow molding process by moving components within ablow mold as known and bringing the internal surface of the parison intocontact with an opposite portion to form a plurality of ribs. These ribscan provide additional structural strength to the blow molded runningboard. In general, any pattern of ribs may be formed so as to providesufficient strength to the running board 102.

Another component as may include the thermoplastic composition processedaccording to a blow molding process is a support structure, an exampleof which is illustrated in FIG. 15. Support structure 110 is a blowmolded hollow, integrally formed structure that can be used to supportboth the radiator and lights of a motor vehicle. The structure 110includes a radiator frame portion 112 and a plurality of apertures 114that can be used for securing a motor vehicle radiator (not shown forsake of clarity) to the support structure 110. A pair of light receivingrecesses 116 of the support structure 110 are constructed and arrangedto mount headlights (not shown for sake of clarity) for the motorvehicle. The recesses 116 having apertures 118 for receiving electricalconnecting portions of the lights. As shown, the support structure 110can be nestingly received with respect to a motor vehicle front end 113.

Tubular components are encompassed herein in addition to risers asdiscussed above. For example, tubular components such as hoses,conduits, flowlines, etc. as may be utilized in carrying automotivefluids including gasoline, oil, coolant, etc. are encompassed herein.Moreover, tubular components as may be blow molded from thethermoplastic composition are not limited to those found in eitherautomotive or oil and gas field applications. Referring to FIG. 16, oneembodiment of a single layer conduit 120 blow molded from thethermoplastic composition is shown. As shown, the conduit 120 extends inmultiple directions leading to a relatively complex shape. For instance,before the thermoplastic composition can solidify, the angulardisplacements as shown in FIG. 16 can be formed into the part. Theconduit 120 includes angular displacement changes at 122, 124 and 126.The conduit may be, for instance, a component that may be used in theexhaust system of a vehicle or the fuel system of the vehicle. Forexample, conduit 120 can form a filler tube for conveying gasoline froma fuel filler neck to a gasoline tank.

As discussed above, the tubular member that incorporates thethermoplastic composition can be a multi-layered tubular member. FIG. 17illustrates a multi-layered tubular member 210 as may incorporate thethermoplastic composition in one or more blow molded layers of thetubular member 210. For example, the inner layer 212 can be formed ofthe blow molded thermoplastic composition that exhibits high impactstrength characteristics under a wide temperature range and that issubstantially inert to the materials to be carried within the tubularmember 210.

The outer layer 214 and the intermediate layer 216 can include athermoplastic composition that is the same or different than thethermoplastic composition that forms the inner layer. In addition, theouter layers of the multi-layered tubular member may be blow molded orformed according to a different formation technique. However, it shouldbe understood that layers of the multilayer tubular member may be formedof a plurality of different materials, and only one or multiple layersof the member may be formed of the thermoplastic composition. Forexample, in one embodiment the intermediate layer 216 can exhibit highresistance to pressure and mechanical effects. By way of example, layer216 can be formed of polyamides from the group of homopolyamides,co-polyamides, their blends or mixtures which each other or with otherpolymers. Alternatively, layer 216 can be formed of a fiber reinforcedmaterial such as a fiber-reinforced resin composite or the like. Forexample, a polyaramid (e.g., Kevlar®) woven mat can be utilized to forman intermediate layer 216 that is highly resistant to mechanicalassaults. Such an intermediate layer may be formed over the pre-formedblow molded inner layer or may be formed first, and the inner layer maybe formed according to a blow molding method on the interior surface ofthe first-formed layer.

Outer layer 214 can provide protection from external assaults as well asprovide insulative or other desirable characteristics to the tubularmember. For example, a multi-layer hose can include an outer layer 214formed from an adequate kind of rubber material having high levels ofchipping, weather, flame and cold resistance. Examples of such materialsinclude thermoplastic elastomer such as polyamide thermoplasticelastomer, polyester thermoplastic elastomer, polyolefin thermoplasticelastomer, and styrene thermoplastic elastomer. Suitable materials forouter layer 214 include, without limitation, ethylene-propylene-dieneterpolymer rubber, ethylene-propylene rubber, chlorosulfonatedpolyethylene rubber, a blend of acrylonitrile-butadiene rubber andpolyvinyl chloride, a blend of acrylonitrile-butadiene rubber andethylene-propylene-diene terpolymer rubber, and chlorinated polyethylenerubber.

Outer layer 214 can alternatively be formed of a harder, less flexiblematerial, such as a polyolefin, polyvinylchloride, or a high densitypolyethylene, a fiber reinforced composite material such as a glassfiber composite or a carbon fiber composite, or a metal material such asa steel jacket. Moreover, the outer layer, as with other layers of amulti-layer member 210, may be blow molded or may be formed according toanother formation technique.

Of course, a multi-layer tubular member is not limited to three layers,and may include two, four, or more distinct layers. A multi-layertubular member may further contain one or more adhesive layers formedfrom adhesive materials such as, for example, polyester polyurethanes,polyether polyurethanes, polyester elastomers, polyether elastomers,polyamides, polyether polyamides, polyether polyimides, functionalizedpolyolefins, and the like.

The blow molded thermoplastic composition can exhibit both flexibilityand high strength characteristics. FIG. 18 schematically illustrates aprocess that can be used in forming the thermoplastic composition. Asillustrated, the components of the thermoplastic composition may bemelt-kneaded in a melt processing unit such as an extruder 300. Extruder300 can be any extruder as is known in the art including, withoutlimitation, a single, twin, or multi-screw extruder, a co-rotating orcounter rotating extruder, an intermeshing or non-intermeshing extruder,and so forth. In one embodiment, the composition may be melt processedin an extruder 300 that includes multiple zones or barrels. In theillustrated embodiment, extruder 300 includes 10 barrels numbered321-330 along the length of the extruder 300, as shown. Each barrel321-330 can include one or more feed lines 314, 316, vents 312,temperature controls, etc. that can be independently operated. A generalpurpose screw design can be used to melt process the thermoplasticcomposition. By way of example, a thermoplastic composition may be meltmixed using a twin screw extruder such as a Coperion co-rotating fullyintermeshing twin screw extruder.

In forming a thermoplastic composition, a polyarylene sulfide can be fedto the extruder 300 at a main feed throat 314. For instance, thepolyarylene sulfide may be fed to the main feed throat 314 at the firstbarrel 321 by means of a metering feeder. The polyarylene sulfide can bemelted and mixed with the other components of the composition as itprogresses through the extruder 300. The impact modifier can be added tothe composition in conjunction with the thermoplastic composition at themain feed throat 314 or downstream of the main feed throat, as desired.

At a point downstream of the main feed throat 314, and followingaddition of the impact modifier to the composition, the crosslinkingagent can be added to the composition. For instance, in the illustratedembodiment, a second feed line 316 at barrel 326 can be utilized foraddition of the crosslinking agent. The point of addition for thecrosslinking agent is not particularly limited. However, thecrosslinking agent can be added to the composition at a point after thepolyarylene sulfide has been mixed with the impact modifier under shearsuch that the impact modifier is well distributed throughout thepolyarylene sulfide.

The polyarylene sulfide may be a polyarylene thioether containing repeatunits of the formula (I):-[(Ar¹)_(n)-X]_(m)-[(Ar²)_(i)-Y]_(j)-[(A³)_(k)-Z]_(l)-[(Ar⁴)_(o)-W]_(p)-  (I)wherein Ar¹, Ar², Ar³, and Ar⁴ are the same or different and are aryleneunits of 6 to 18 carbon atoms; W, X, Y, and Z are the same or differentand are bivalent linking groups selected from —SO₂—, —S—, —SO—, —CO—,—O—, —COO— or alkylene or alkylidene groups of 1 to 6 carbon atoms andwherein at least one of the linking groups is —S—; and n, m, i, j, k, l,o, and p are independently zero or 1, 2, 3, or 4, subject to the provisothat their sum total is not less than 2. The arylene units Ar¹, Ar²,Ar³, and Ar⁴ may be selectively substituted or unsubstituted.Advantageous arylene systems are phenylene, biphenylene, naphthylene,anthracene and phenanthrene. The polyarylene sulfide typically includesmore than about 30 mol %, more than about 50 mol %, or more than about70 mol % arylene sulfide (—S—) units. In one embodiment the polyarylenesulfide includes at least 85 mol % sulfide linkages attached directly totwo aromatic rings.

In one embodiment, the polyarylene sulfide is a polyphenylene sulfide,defined herein as containing the phenylene sulfide structure—(C₆H₄—S)_(n)— (wherein n is an integer of 1 or more) as a componentthereof.

The polyarylene sulfide may be synthesized prior to forming thethermoplastic composition, though this is not a requirement of aprocess. For example, a polyarylene sulfide can be purchased from knownsuppliers. For instance Fortron® polyphenylene sulfide available fromTicona of Florence, Ky., USA can be purchased and utilized as thepolyarylene sulfide. When the polyarylene sulfide is synthesize,synthesis techniques as are generally known in the art may be utilized.By way of example, a process for producing a polyarylene sulfide caninclude reacting a material that provides a hydrosulfide ion, e.g., analkali metal sulfide, with a dihaloaromatic compound in an organic amidesolvent.

The alkali metal sulfide can be, for example, lithium sulfide, sodiumsulfide, potassium sulfide, rubidium sulfide, cesium sulfide or amixture thereof. When the alkali metal sulfide is a hydrate or anaqueous mixture, the alkali metal sulfide can be processed according toa dehydrating operation in advance of the polymerization reaction. Analkali metal sulfide can also be generated in situ. In addition, a smallamount of an alkali metal hydroxide can be included in the reaction toremove or react impurities (e.g., to change such impurities to harmlessmaterials) such as an alkali metal polysulfide or an alkali metalthiosulfate, which may be present in a very small amount with the alkalimetal sulfide.

The dihaloaromatic compound can be, without limitation, ano-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene,dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoicacid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenylsulfoxide or dihalodiphenyl ketone. Dihaloaromatic compounds may be usedeither singly or in any combination thereof. Specific exemplarydihaloaromatic compounds can include, without limitation,p-dichlorobenzene; m-dichlorobenzene; o-dichlorobenzene;2,5-dichlorotoluene; 1,4-dibromobenzene; 1,4-dichloronaphthalene;1-methoxy-2,5-dichlorobenzene; 4,4′-dichlorobiphenyl;3,5-dichlorobenzoic acid; 4,4′-dichlorodiphenyl ether;4,4′-dichlorodiphenylsulfone; 4,4′-dichlorodiphenylsulfoxide; and4,4′-dichlorodiphenyl ketone.

The halogen atom can be fluorine, chlorine, bromine or iodine, and 2halogen atoms in the same dihalo-aromatic compound may be the same ordifferent from each other. In one embodiment, o-dichlorobenzene,m-dichlorobenzene, p-dichlorobenzene or a mixture of 2 or more compoundsthereof is used as the dihalo-aromatic compound.

As is known in the art, it is also possible to use a monohalo compound(not necessarily an aromatic compound) in combination with thedihaloaromatic compound in order to form end groups of the polyarylenesulfide or to regulate the polymerization reaction and/or the molecularweight of the polyarylene sulfide.

The polyarylene sulfide may be a homopolymer or may be a copolymer. By asuitable, selective combination of dihaloaromatic compounds, apolyarylene sulfide copolymer can be formed containing not less than twodifferent units. For instance, in the case where p-dichlorobenzene isused in combination with m-dichlorobenzene or4,4′-dichlorodiphenylsulfone, a polyarylene sulfide copolymer can beformed containing segments having the structure of formula (II):

and segments having the structure of formula (III):

or segments having the structure of formula (IV):

In general, the amount of the dihaloaromatic compound(s) per mole of theeffective amount of the charged alkali metal sulfide can generally befrom 1.0 to 2.0 moles, from 1.05 to 2.0 moles, or from 1.1 to 1.7 moles.Thus, the polyarylene sulfide can include alkyl halide (generally alkylchloride) end groups.

A process for producing the polyarylene sulfide can include carrying outthe polymerization reaction in an organic amide solvent. Exemplaryorganic amide solvents used in a polymerization reaction can include,without limitation, N-methyl-2-pyrrolidone; N-ethyl-2-pyrrolidone;N,N-dimethylformamide; N,N-dimethylacetamide; N-methylcaprolactam;tetramethylurea; dimethylimidazolidinone; hexamethyl phosphoric acidtriamide and mixtures thereof. The amount of the organic amide solventused in the reaction can be, e.g., from 0.2 to 5 kilograms per mole(kg/mol) of the effective amount of the alkali metal sulfide.

The polymerization can be carried out by a step-wise polymerizationprocess. The first polymerization step can include introducing thedihaloaromatic compound to a reactor, and subjecting the dihaloaromaticcompound to a polymerization reaction in the presence of water at atemperature of from about 180° C. to about 235° C., or from about 200°C. to about 230° C., and continuing polymerization until the conversionrate of the dihaloaromatic compound attains to not less than about 50mol % of the theoretically necessary amount.

In a second polymerization step, water is added to the reaction slurryso that the total amount of water in the polymerization system isincreased to about 7 moles, or to about 5 moles, per mole of theeffective amount of the charged alkali metal sulfide. Following, thereaction mixture of the polymerization system can be heated to atemperature of from about 250° C. to about 290° C., from about 255° C.to about 280° C., or from about 260° C. to about 270° C. and thepolymerization can continue until the melt viscosity of the thus formedpolymer is raised to the desired final level of the polyarylene sulfide.The duration of the second polymerization step can be, e.g., from about0.5 to about 20 hours, or from about 1 to about 10 hours.

The polyarylene sulfide may be linear, semi-linear, branched orcrosslinked. A linear polyarylene sulfide includes as the mainconstituting unit the repeating unit of —(Ar—S)—. In general, a linearpolyarylene sulfide may include about 80 mol % or more of this repeatingunit. A linear polyarylene sulfide may include a small amount of abranching unit or a cross-linking unit, but the amount of branching orcross-linking units may be less than about 1 mol % of the total monomerunits of the polyarylene sulfide. A linear polyarylene sulfide polymermay be a random copolymer or a block copolymer containing theabove-mentioned repeating unit.

A semi-linear polyarylene sulfide may be utilized that may have across-linking structure or a branched structure provided by introducinginto the polymer a small amount of one or more monomers having three ormore reactive functional groups. For instance between about 1 mol % andabout 10 mol % of the polymer may be formed from monomers having threeor more reactive functional groups. Methods that may be used in makingsemi-linear polyarylene sulfide are generally known in the art. By wayof example, monomer components used in forming a semi-linear polyarylenesulfide can include an amount of polyhaloaromatic compounds having 2 ormore halogen substituents per molecule which can be utilized inpreparing branched polymers. Such monomers can be represented by theformula R′X_(n), where each X is selected from chlorine, bromine, andiodine, n is an integer of 3 to 6, and R′ is a polyvalent aromaticradical of valence n which can have up to about 4 methyl substituents,the total number of carbon atoms in R′ being within the range of 6 toabout 16. Examples of some polyhaloaromatic compounds having more thantwo halogens substituted per molecule that can be employed in forming asemi-linear polyarylene sulfide include 1,2,3-trichlorobenzene,1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene,1,2,4-triiodobenzene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene,1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2′,4,4′-tetrachlorobiphenyl,2,2′,5,5′-tetra-iodobiphenyl,2,2′,6,6′-tetrabromo-3,3′,5,5′-tetramethylbiphenyl,1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, andthe like, and mixtures thereof.

Following polymerization, the polyarylene sulfide may be washed withliquid media. For instance, the polyarylene sulfide may be washed withwater and/or organic solvents that will not decompose the polyarylenesulfide including, without limitation, acetone, N-methyl-2-pyrrolidone,a salt solution, and/or an acidic media such as acetic acid orhydrochloric acid prior to combination with other components whileforming the mixture. The polyarylene sulfide can be washed in asequential manner that is generally known to persons skilled in the art.Washing with an acidic solution or a salt solution may reduce thesodium, lithium or calcium metal ion end group concentration from about2000 ppm to about 100 ppm.

A polyarylene sulfide can be subjected to a hot water washing process.The temperature of a hot water wash can be at or above about 100° C.,for instance higher than about 120° C., higher than about 150° C., orhigher than about 170° C.

The polymerization reaction apparatus for forming the polyarylenesulfide is not especially limited, although it is typically desired toemploy an apparatus that is commonly used in formation of high viscosityfluids. Examples of such a reaction apparatus may include a stirringtank type polymerization reaction apparatus having a stirring devicethat has a variously shaped stirring blade, such as an anchor type, amultistage type, a spiral-ribbon type, a screw shaft type and the like,or a modified shape thereof. Further examples of such a reactionapparatus include a mixing apparatus commonly used in kneading, such asa kneader, a roll mill, a Banbury mixer, etc. Following polymerization,the molten polyarylene sulfide may be discharged from the reactor,typically through an extrusion orifice fitted with a die of desiredconfiguration, cooled, and collected. Commonly, the polyarylene sulfidemay be discharged through a perforated die to form strands that aretaken up in a water bath, pelletized and dried. The polyarylene sulfidemay also be in the form of a strand, granule, or powder.

The thermoplastic composition may include the polyarylene sulfidecomponent (which also encompasses a blend of polyarylene sulfides) in anamount from about 10 wt. % to about 99 wt. % by weight of thecomposition, for instance from about 20% wt. % to about 90 wt. % byweight of the composition.

The polyarylene sulfide may be of any suitable molecular weight and meltviscosity, generally depending upon the final application intended forthe thermoplastic composition. For instance, the melt viscosity of thepolyarylene sulfide may be a low viscosity polyarylene sulfide, having amelt viscosity of less than about 500 poise, a medium viscositypolyarylene sulfide, having a melt viscosity of between about 500 poiseand about 1500 poise, or a high melt viscosity polyarylene sulfide,having a melt viscosity of greater than about 1,500 poise, as determinedin accordance with ISO Test No. 11443 at a shear rate of 1200 s⁻¹ and ata temperature of 310° C.

According to one embodiment, the polyarylene sulfide can befunctionalized to further encourage bond formation between thepolyarylene sulfide and the impact modifier, which can further improvedistribution of the impact modifier throughout the composition andfurther prevent phase separation. For instance, a polyarylene sulfidecan be further treated following formation with a carboxyl, acidanhydride, amine, isocyanate or other functional group-containingmodifying compound to provide a functional terminal group on thepolyarylene sulfide. By way of example, a polyarylene sulfide can bereacted with a modifying compound containing a mercapto group or adisulfide group and also containing a reactive functional group. In oneembodiment, the polyarylene sulfide can be reacted with the modifyingcompound in an organic solvent. In another embodiment, the polyarylenesulfide can be reacted with the modifying compound in the molten state.

In one embodiment, a disulfide compound containing the desiredfunctional group can be incorporated into the thermoplastic compositionformation process, and the polyarylene sulfide can be functionalized inconjunction with formation of the composition. For instance, a disulfidecompound containing the desired reactive functional groups can be addedto the melt extruder in conjunction with the polyarylene sulfide or atany other point prior to or in conjunction with the addition of thecrosslinking agent.

Reaction between the polyarylene sulfide polymer and the reactivelyfunctionalized disulfide compound can include chain scission of thepolyarylene sulfide polymer that can decrease melt viscosity of thepolyarylene sulfide. In one embodiment, a higher melt viscositypolyarylene sulfide having low halogen content can be utilized as astarting polymer. Following reactive functionalization of thepolyarylene sulfide polymer by use of a functional disulfide compound, arelatively low melt viscosity polyarylene sulfide with low halogencontent can be formed. Following this chain scission, the melt viscosityof the polyarylene sulfide can be suitable for further processing, andthe overall halogen content of the low melt viscosity polyarylenesulfide can be quite low. A thermoplastic composition that exhibitsexcellent strength and degradation resistance in addition to low halogencontent can be advantageous as low halogen content polymeric materialsare becoming increasingly desired due to environmental concerns. In oneembodiment, the thermoplastic composition can have a halogen content ofless than about 1000 ppm, less than about 900 ppm, less than about 600ppm, or less than about 400 ppm as determined according to an elementalanalysis using Parr Bomb combustion followed by Ion Chromatography.

The disulfide compound can generally have the structure of:R¹—S—S—R²wherein R¹ and R² may be the same or different and are hydrocarbongroups that independently include from 1 to about 20 carbons. Forinstance, R¹ and R² may be an alkyl, cycloalkyl, aryl, or heterocyclicgroup. R¹ and R¹ may include reactive functionality at terminal end(s)of the disulfide compound. For example, at least one of R¹ and R² mayinclude a terminal carboxyl group, hydroxyl group, a substituted ornon-substituted amino group, a nitro group, or the like. In general, thereactive functionality can be selected such that the reactivelyfunctionalized polyarylene sulfide can react with the impact modifier.For example, when considering an epoxy-terminated impact modifier, thedisulfide compound can include carboxyl and/or amine functionality.

Examples of disulfide compounds including reactive terminal groups asmay be encompassed herein may include, without limitation,2,2′-diaminodiphenyl disulfide, 3,3′-diaminodiphenyl disulfide,4,4′-diaminodiphenyl disulfide, dibenzyl disulfide, dithiosalicyclicacid, dithioglycolic acid, α,α′-dithiodilactic acid, β,β′-dithiodilacticacid, 3,3′-dithiodipyridine, 4,4′dithiomorpholine,2,2′-dithiobis(benzothiazole), 2,2′-dithiobis(benzimidazole),2,2′-dithiobis(benzoxazole) and 2-(4′-morpholinodithio)benzothiazole.

The ratio of the amount of the polyarylene sulfide to the amount of thedisulfide compound can be from about 1000:1 to about 10:1, from about500:1 to about 20:1, or from about 400:1 to about 30:1.

In addition to the polyarylene sulfide polymer, the composition alsoincludes an impact modifier. More specifically, the impact modifier canbe an olefinic copolymer or terpolymer. For instance, the impactmodifier can include ethylenically unsaturated monomer units have fromabout 4 to about 10 carbon atoms.

The impact modifier can be modified to include functionalization so asto react with the crosslinking agent. For instance, the impact modifiercan be modified with a mole fraction of from about 0.01 to about 0.5 ofone or more of the following: an α, β unsaturated dicarboxylic acid orsalt thereof having from about 3 to about 8 carbon atoms; an α, βunsaturated carboxylic acid or salt thereof having from about 3 to about8 carbon atoms; an anhydride or salt thereof having from about 3 toabout 8 carbon atoms; a monoester or salt thereof having from about 3 toabout 8 carbon atoms; a sulfonic acid or a salt thereof; an unsaturatedepoxy compound having from about 4 to about 11 carbon atoms. Examples ofsuch modification functionalities include maleic anhydride, fumaricacid, maleic acid, methacrylic acid, acrylic acid, and glycidylmethacrylate. Examples of metallic acid salts include the alkaline metaland transitional metal salts such as sodium, zinc, and aluminum salts.

A non-limiting listing of impact modifiers that may be used includeethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymers,ethylene-alkyl (meth)acrylate-maleic anhydride terpolymers,ethylene-alkyl (meth)acrylate-glycidyl (meth)acrylate terpolymers,ethylene-acrylic ester-methacrylic acid terpolymer, ethylene-acrylicester-maleic anhydride terpolymer, ethylene-methacrylic acid-methacrylicacid alkaline metal salt (ionomer) terpolymers, and the like. In oneembodiment, for instance, an impact modifier can include a randomterpolymer of ethylene, methylacrylate, and glycidyl methacrylate. Theterpolymer can have a glycidyl methacrylate content of from about 5% toabout 20%, such as from about 6% to about 10%. The terpolymer may have amethylacrylate content of from about 20% to about 30%, such as about24%.

According to one embodiment, the impact modifier may be a linear orbranched, homopolymer or copolymer (e.g., random, graft, block, etc.)containing epoxy functionalization, e.g., terminal epoxy groups,skeletal oxirane units, and/or pendent epoxy groups. For instance, theimpact modifier may be a copolymer including at least one monomercomponent that includes epoxy functionalization. The monomer units ofthe impact modifier may vary. In one embodiment, for example, the impactmodifier can include epoxy-functional methacrylic monomer units. As usedherein, the term methacrylic generally refers to both acrylic andmethacrylic monomers, as well as salts and esters thereof, e.g.,acrylate and methacrylate monomers. Epoxy-functional methacrylicmonomers as may be incorporated in the impact modifier may include, butare not limited to, those containing 1,2-epoxy groups, such as glycidylacrylate and glycidyl methacrylate. Other suitable epoxy-functionalmonomers include allyl glycidyl ether, glycidyl ethacrylate, andglycidyl itoconate.

Other monomer units may additionally or alternatively be a component ofthe impact modifier. Examples of other monomers may include, forexample, ester monomers, olefin monomers, amide monomers, etc. In oneembodiment, the impact modifier can include at least one linear orbranched α-olefin monomer, such as those having from 2 to 20 carbonatoms, or from 2 to 8 carbon atoms. Specific examples include ethylene;propylene; 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene;1-pentene; 1-pentene with one or more methyl, ethyl or propylsubstituents; 1-hexene with one or more methyl, ethyl or propylsubstituents; 1-heptene with one or more methyl, ethyl or propylsubstituents; 1-octene with one or more methyl, ethyl or propylsubstituents; 1-nonene with one or more methyl, ethyl or propylsubstituents; ethyl, methyl or dimethyl-substituted 1-decene;1-dodecene; and styrene.

Monomers included in an impact modifier that includes epoxyfunctionalization can include monomers that do not include epoxyfunctionalization, as long as at least a portion of the monomer units ofthe polymer are epoxy functionalized.

In one embodiment, the impact modifier can be a terpolymer that includesepoxy functionalization. For instance, the impact modifier can include amethacrylic component that includes epoxy functionalization, an α-olefincomponent, and a methacrylic component that does not include epoxyfunctionalization. For example, the impact modifier may bepoly(ethylene-co-methylacrylate-co-glycidyl methacrylate), which has thefollowing structure:

wherein, a, b, and c are 1 or greater.

In another embodiment the impact modifier can be a random copolymer ofethylene, ethyl acrylate and maleic anhydride having the followingstructure:

wherein x, y and z are 1 or greater.

The relative proportion of the various monomer components of acopolymeric impact modifier is not particularly limited. For instance,in one embodiment, the epoxy-functional methacrylic monomer componentscan form from about 1 wt. % to about 25 wt. %, or from about 2 wt. % toabout 20 wt % of a copolymeric impact modifier. An a-olefin monomer canform from about 55 wt. % to about 95 wt. %, or from about 60 wt. % toabout 90 wt. %, of a copolymeric impact modifier. When employed, othermonomeric components (e.g., a non-epoxy functional methacrylic monomers)may constitute from about 5 wt. % to about 35 wt. %, or from about 8 wt.% to about 30 wt. %, of a copolymeric impact modifier.

An impact modifier may be formed according to standard polymerizationmethods as are generally known in the art. For example, a monomercontaining polar functional groups may be grafted onto a polymerbackbone to form a graft copolymer. Alternatively, a monomer containingfunctional groups may be copolymerized with a monomer to form a block orrandom copolymer using known free radical polymerization techniques,such as high pressure reactions, Ziegler-Natta catalyst reactionsystems, single site catalyst (e.g., metallocene) reaction systems, etc.

Alternatively, an impact modifier may be obtained on the retail market.By way of example, suitable compounds for use as an impact modifier maybe obtained from Arkema under the name Lotader®.

The molecular weight of the impact modifier can vary widely. Forexample, the impact modifier can have a number average molecular weightfrom about 7,500 to about 250,000 grams per mole, in some embodimentsfrom about 15,000 to about 150,000 grams per mole, and in someembodiments, from about 20,000 to 100,000 grams per mole, with apolydispersity index typically ranging from 2.5 to 7.

In general, the impact modifier may be present in the composition in anamount from about 0.05% to about 40% by weight, from about 0.05% toabout 37% by weight, or from about 0.1% to about 35% by weight.

Referring again to FIG. 18, the impact modifier can be added to thecomposition in conjunction with the polyarylene sulfide at the main feedthroat 314 of the melt processing unit. This is not a requirement of thecomposition formation process, however, and in other embodiments, theimpact modifier can be added downstream of the main feed throat. Forinstance, the impact modifier may be added at a location downstream fromthe point at which the polyarylene sulfide is supplied to the meltprocessing unit, but yet prior to the melting section, i.e., that lengthof the melt processing unit in which the polyarylene sulfide becomesmolten. In another embodiment, the impact modifier may be added at alocation downstream from the point at which the polyarylene sulfidebecomes molten.

If desired, one or more distributive and/or dispersive mixing elementsmay be employed within the mixing section of the melt processing unit.Suitable distributive mixers for single screw extruders may include butare not limited to, for instance, Saxon, Dulmage, Cavity Transfermixers, etc. Likewise, suitable dispersive mixers may include but arenot limited to Blister ring, Leroy/Maddock, CRD mixers, etc. As is wellknown in the art, the mixing may be further improved by using pins inthe barrel that create a folding and reorientation of the polymer melt,such as those used in Buss Kneader extruders, Cavity Transfer mixers,and Vortex Intermeshing Pin mixers.

In addition to the polyarylene sulfide and the impact modifier, thethermoplastic composition can include a crosslinking agent. Thecrosslinking agent can be a polyfunctional compound or combinationthereof that can react with functionality of the impact modifier to formcrosslinks within and among the polymer chains of the impact modifier.In general, the crosslinking agent can be a non-polymeric compound,i.e., a molecular compound that includes two or more reactivelyfunctional terminal moieties linked by a bond or a non-polymeric(non-repeating) linking component. By way of example, the crosslinkingagent can include but is not limited to di-epoxides, poly-functionalepoxides, diisocyanates, polyisocyanates, polyhydric alcohols,water-soluble carbodiimides, diamines, diaminoalkanes, polyfunctionalcarboxylic acids, diacid halides, and so forth. For instance, whenconsidering an epoxy-functional impact modifier, a non-polymericpolyfunctional carboxylic acid or amine can be utilized as acrosslinking agent.

Specific examples of polyfunctional carboxylic acid crosslinking agentscan include, without limitation, isophthalic acid, terephthalic acid,phthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenylether, 4,4′-bisbenzoic acid, 1,4- or 1,5-naphthalene dicarboxylic acids,decahydronaphthalene dicarboxylic acids, norbornene dicarboxylic acids,bicyclooctane dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid (bothcis and trans), 1,4-hexylenedicarboxylic acid, adipic acid, azelaicacid, dicarboxyl dodecanoic acid, succinic acid, maleic acid, glutaricacid, suberic acid, azelaic acid and sebacic acid. The correspondingdicarboxylic acid derivatives, such as carboxylic acid diesters havingfrom 1 to 4 carton atoms in the alcohol radical, carboxylic acidanhydrides or carboxylic acid halides may also be utilized.

Exemplary diols useful as crosslinking agents can include, withoutlimitation, aliphatic diols such as ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propane diol,2-ethyl-2-methyl-1,3-propane diol, 1,4-butane diol, 1,4-but-2-ene diol,1,3-1,5-pentane diol, 1,5-pentane diol, dipropylene glycol,2-methyl-1,5-pentane diol, and the like. Aromatic diols can also beutilized such as, without limitation, hydroquinone, catechol,resorcinol, methylhydroquinone, chlorohydroquinone, bisphenol A,tetrachlorobisphenol A, phenolphthalein, and the like. Exemplarycycloaliphatic diols as may be used include a cycloaliphatic moiety, forexample 1,6-hexane diol, dimethanol decalin, dimethanol bicyclooctane,1,4-cyclohexane dimethanol (including its cis- and trans-isomers),triethylene glycol, 1,10-decanediol, and the like.

Exemplary diamines that may be utilized as crosslinking agents caninclude, without limitation, isophorone-diamine, ethylenediamine, 1,2-,1,3-propylene-diamine, N-methyl-1,3-propylene-diamine,N,N′-dimethyl-ethylene-diamine, and aromatic diamines, such as, forexample, 2,4- and 2,6-toluoylene-diamine, 3,5-diethyl-2,4- and/or-2,6-toluoylene-diamine, and primary ortho- di-, tri- and/ortetra-alkyl-substituted 4,4′-diaminodiphenyl-methanes. (cyclo)aliphaticdiamines, such as, for example, isophorone-diamine, ethylenediamine,1,2-, 1,3-propylene-diamine, N-methyl-1,3-propylene-diamine,N,N′-dimethyl-ethylene-diamine, and aromatic diamines, such as, forexample, 2,4- and 2,6-toluoylene-diamine, 3,5-diethyl-2,4- and/or-2,6-toluoylene-diamine, and primary ortho- di-, tri- and/ortetra-alkyl-substituted 4,4′-diaminodiphenyl-methanes.

In one embodiment, the composition can include a disulfide-freecrosslinking agent. For example, the crosslinking agent can includecarboxyl and/or amine functionality with no disulfide group that mayreact with the polyarylene sulfide. A crosslinking agent that isdisulfide-free can be utilized so as to avoid excessive chain scissionof the polyarylene sulfide by the crosslinking agent during formation ofthe composition. It should be understood, however, that the utilizationof a disulfide-free crosslinking agent does not in any way limit theutilization of a reactively functionalized disulfide compound forfunctionalizing the polyarylene sulfide. For instance, in oneembodiment, the composition can be formed according to a process thatincludes addition of a reactively functionalized disulfide compound tothe melt processing unit that can reactively functionalize thepolyarylene sulfide. The crosslinking agent utilized in this embodimentcan then be a disulfide-free crosslinking agent that can includefunctionality that is reactive with the impact modifier as well as withthe reactively functionalized polyarylene sulfide. Thus, the compositioncan be highly crosslinked without excessive scission of the polyarylenesulfide polymer chains.

In another embodiment the crosslinking agent and the polyarylene sulfidefunctionalization compound (when present) can be selected so as toencourage chain scission of the polyarylene sulfide. This may bebeneficial, for instance, which chain scission is desired to decreasethe melt viscosity of the polyarylene sulfide polymer.

The thermoplastic composition may generally include the crosslinkingagent in an amount from about 0.05 wt. % to about 2 wt. % by weight ofthe thermoplastic composition, from about 0.07 wt. % to about 1.5 wt. %by weight of the thermoplastic composition, or from about 0.1 wt. % toabout 1.3 wt. %.

The crosslinking agent can be added to the melt processing unitfollowing mixing of the polyarylene sulfide and the impact modifier. Forinstance, as illustrated in FIG. 18, the crosslinking agent can be addedto the composition at a downstream location 316 following addition ofpolyarylene sulfide and the impact modifier (either together orseparately) to the melt processing unit. This can ensure that the impactmodifier has become dispersed throughout the polyarylene sulfide priorto addition of the crosslinking agent.

To help encourage distribution of the impact modifier throughout themelt prior to addition of the crosslinking agent, a variety of differentparameters may be selectively controlled. For example, the ratio of thelength (“L”) to diameter (“D”) of a screw of the melt processing unitmay be selected to achieve an optimum balance between throughput andimpact modifier distribution. For example, the L/D value after the pointat which the impact modifier is supplied may be controlled to encouragedistribution of the impact modifier. More particularly, the screw has ablending length (“L_(B)”) that is defined from the point at which boththe impact modifier and the polyarylene sulfide are supplied to the unit(i.e., either where they are both supplied in conjunction with oneanother or the point at which the latter of the two is supplied) to thepoint at which the crosslinking agent is supplied, the blending lengthgenerally being less than the total length of the screw. For example,when considering a melt processing unit that has an overall L/D of 40,the La/D ratio of the screw can be from about 1 to about 36, in someembodiments from about 4 to about 20, and in some embodiments, fromabout 5 to about 15. In one embodiment, the L/L_(B) ratio can be fromabout 40 to about 1.1, from about 20 to about 2, or from about 10 toabout 5.

Following addition of the crosslinking agent, the composition can bemixed to distribute the crosslinking agent throughout the compositionand encourage reaction between the crosslinking agent, the impactmodifier, and, in one embodiment, with the polyarylene sulfide.

The composition can also include one or more additives as are generallyknown in the art. For example, one or more fillers can be included inthe composition. One or more fillers may generally be included in thecomposition an amount of from about 5 wt. % to about 70 wt. %, or fromabout 20 wt. % to about 65 wt. % by weight of the composition.

The filler can be added to the thermoplastic composition according tostandard practice. For instance, the filler can be added to thecomposition at a downstream location of the melt processing unit. Forexample, a filler may be added to the composition in conjunction withthe addition of the crosslinking agent. However, this is not arequirement of a formation process and the filler can be addedseparately from the crosslinking agent and either upstream or downstreamof the point of addition of the crosslinking agent. In addition, afiller can be added at a single feed location, or may be split and addedat multiple feed locations along the melt processing unit.

In one embodiment, a fibrous filler can be included in the thermoplasticcomposition. The fibrous filler may include one or more fiber typesincluding, without limitation, polymer fibers, glass fibers, carbonfibers, metal fibers, basalt fibers, and so forth, or a combination offiber types. In one embodiment, the fibers may be chopped fibers,continuous fibers, or fiber rovings (tows).

Fiber sizes can vary as is known in the art. In one embodiment, thefibers can have an initial length of from about 3 mm to about 5 mm. Inanother embodiment, for instance when considering a pultrusion process,the fibers can be continuous fibers. Fiber diameters can vary dependingupon the particular fiber used. The fibers, for instance, can have adiameter of less than about 100 μm, such as less than about 50 μm. Forinstance, the fibers can be chopped or continuous fibers and can have afiber diameter of from about 5 μm to about 50 μm, such as from about 5μm to about 15 μm.

The fibers may be pretreated with a sizing as is generally known. In oneembodiment, the fibers may have a high yield or small K numbers. The towis indicated by the yield or K number. For instance, glass fiber towsmay have 50 yield and up, for instance from about 115 yield to about1200 yield.

Other fillers can alternatively be utilized or may be utilized inconjunction with a fibrous filler. For instance, a particulate fillercan be incorporated in the composition. In general, particulate fillerscan encompass any particulate material having a median particle size ofless than about 750 μm, for instance less than about 500 μm, or lessthan about 100 μm. In one embodiment, a particulate filler can have amedian particle size in the range of from about 3 μm to about 20 μm. Inaddition, a particulate filler can be solid or hollow, as is known.Particulate fillers can also include a surface treatment, as is known inthe art.

Particulate fillers can encompass one or more mineral fillers. Forinstance, the thermoplastic composition can include one or more mineralfillers in an amount of from about 1 wt. % to about 60 wt. % of thecomposition. Mineral fillers may include, without limitation, silica,quartz powder, silicates such as calcium silicate, aluminum silicate,kaolin, talc, mica, clay, diatomaceous earth, wollastonite, calciumcarbonate, and so forth.

A filler can be an electrically conductive filler such as, withoutlimitation, carton black, graphite, graphene, carbon fiber, carbonnanotubes, a metal powder, and so forth. In those embodiments in whichthe thermoplastic composition includes electrically conductive fillers,for instance when the thermoplastic composition is utilized in forming afuel line, adequate electrically conductive filler can be included suchthat the composition has a volume specific resistance of equal to orless than about 10⁹ ohms cm.

When incorporating multiple fillers, for instance a particulate fillerand a fibrous filler, the fillers may be added together or separately tothe melt processing unit. For instance, a particulate filler can beadded to the main feed with the polyarylene sulfide or downstream priorto addition of a fibrous filler, and a fibrous filler can be addedfurther downstream of the addition point of the particulate filler. Ingeneral, a fibrous filler can be added downstream of any other fillerssuch as a particulate filler, though this is not a requirement.

In one embodiment, the thermoplastic composition can include a UVstabilizer as an additive. For instance, the thermoplastic compositioncan include a UV stabilizer in an amount of between about 0.5 wt. % andabout 15 wt. %, between about 1 wt. % and about 8 wt. %, or betweenabout 1.5 wt. % and about 7 wt. % of a UV stabilizer. One particularlysuitable UV stabilizer that may be employed is a hindered amine UVstabilizer. Suitable hindered amine UV stabilizer compounds may bederived from a substituted piperidine, such as alkyl-substitutedpiperidyl, piperidinyl, piperazinone, alkoxypiperidinyl compounds, andso forth. For example, the hindered amine may be derived from a2,2,6,6-tetraalkylpiperidinyl. The hindered amine may, for example, bean oligomeric or polymeric compound having a number average molecularweight of about 1,000 or more, in some embodiments from about 1000 toabout 20,000, in some embodiments from about 1500 to about 15,000, andin some embodiments, from about 2000 to about 5000. Such compoundstypically contain at least one 2,2,6,6-tetraalkylpiperidinyl group(e.g., 1 to 4) per polymer repeating unit. One particularly suitablehigh molecular weight hindered amine is commercially available fromClariant under the designation Hostavin® N30 (number average molecularweight of 1200). Another suitable high molecular weight hindered amineis commercially available from Adeka Palmarole SAS under the designationADK STAB® LA-63 and ADK STAB® LA-68.

In addition to the high molecular hindered amines, low molecular weighthindered amines may also be employed. Such hindered amines are generallymonomeric in nature and have a molecular weight of about 1000 or less,in some embodiments from about 155 to about 800, and in someembodiments, from about 300 to about 800.

Other suitable UV stabilizers may include UV absorbers, such asbenzotriazoles or benzopheones, which can absorb UV radiation.

An additive that may be included in a thermoplastic composition is oneor more colorants as are generally known in the art. For instance, thecomposition can include from about 0.1 wt. % to about 10 wt. %, or fromabout 0.2 wt. % to about 5 wt. % of one or more colorants. As utilizedherein, the term “colorant” generally refers to any substance that canimpart color to a material. Thus, the term “colorant” encompasses bothdyes, which exhibit solubility in an aqueous solution, and pigments,that exhibit little or no solubility in an aqueous solution.

Examples of dyes that may be used include, but are not limited to,disperse dyes. Suitable disperse dyes may include those described in“Disperse Dyes” in the Color Index, 3^(rd) edition. Such dyes include,for example, carboxylic acid group-free and/or sulfonic acid group-freenitro, amino, aminoketone, ketoninime, methine, polymethine,diphenylamine, quinoline, benzimidazole, xanthene, oxazine and coumarindyes, anthraquinone and azo dyes, such as mono- or di-azo dyes. Dispersedyes also include primary red color disperse dyes, primary blue colordisperse dyes, and primary yellow color dyes

Pigments that can be incorporated in a thermoplastic composition caninclude, without limitation, organic pigments, inorganic pigments,metallic pigments, phosphorescent pigments, fluorescent pigments,photochromic pigments, thermochromic pigments, iridescent pigments, andpearlescent pigments. The specific amount of pigment can depends uponthe desired final color of the product. Pastel colors are generallyachieved with the addition of titanium dioxide white or a similar whitepigment to a colored pigment.

Other additives that can be included in the thermoplastic compositioncan encompass, without limitation, antimicrobials, lubricants, pigmentsor other colorants, impact modifiers, antioxidants, stabilizers (e.g.,heat stabilizers including organophosphites such as Doverphos® productsavailable from Dover Chemical Corporation), surfactants, flow promoters,solid solvents, and other materials added to enhance properties andprocessability. Such optional materials may be employed in thethermoplastic composition in conventional amounts and according toconventional processing techniques, for instance through addition to thethermoplastic composition at the main feed throat. Beneficially, thethermoplastic composition can exhibit desirable characteristics withoutthe addition of plasticizers. For instance, the composition can be freeof plasticizers such as phthalate esters, trimellitates, sebacates,adipates, gluterates, azelates, maleates, benzoates, and so forth.

Following addition of all components to the thermoplastic composition,the composition is thoroughly mixed in the remaining section(s) of theextruder and extruded through a die. The final extrudate can bepelletized and stored prior to blow molding or may be directly fed tothe blow molding process.

Embodiments of the present disclosure are illustrated by the followingexamples that are merely for the purpose of illustration of embodimentsand are not to be regarded as limiting the scope of the invention or themanner in which it may be practiced. Unless specifically indicatedotherwise, parts and percentages are given by weight.

Formation and Test Methods

Injection Molding Process: Tensile bars are injection molded to ISO527-1 specifications according to standard ISO conditions.

Melt Viscosity: All materials are dried for 1.5 hours at 150° C. undervacuum prior to testing. The melt viscosity is measured on a capillaryrheometer at 316° C. and 400 sec⁻¹ with the viscosity measurement takenafter five minutes of constant shear.

Tensile Properties: Tensile properties including tensile modulus, yieldstress, yield strain, strength at break, elongation at yield, elongationat break, etc. are tested according to ISO Test No. 527 (technicallyequivalent to ASTM D638). Modulus, strain, and strength measurements aremade on the same test strip sample having a length of 80 mm, thicknessof 10 mm, and width of 4 mm. The testing temperature is 23° C., and thetesting speeds are 5 or 50 mm/min.

Flexural Properties: Flexural properties including flexural strength andflexural modulus are tested according to ISO Test No. 178 (technicallyequivalent to ASTM D790). This test is performed on a 64 mm supportspan. Tests are run on the center portions of uncut ISO 3167multi-purpose bars. The testing temperature is 23° C. and the testingspeed is 2 mm/min.

Deflection Temperature Under Load (“DTUL”): The deflection under loadtemperature was determined in accordance with ISO Test No. 75-2(technically equivalent to ASTM D648-07). More particularly, a teststrip sample having a length of 80 mm, thickness of 10 mm, and width of4 mm was subjected to an edgewise three-point bending test in which thespecified load (maximum outer fibers stress) was 1.8 Megapascals. Thespecimen was lowered into a silicone oil bath where the temperature israised at 2° C. per minute until it deflects 0.25 mm (0.32 mm for ISOTest No. 75-2).

Notched Charpy Impact Strength: Notched Charpy properties are testedaccording to ISO Test No. ISO 179-1) (technically equivalent to ASTMD256, Method B). This test is run using a Type A notch (0.25 mm baseradius) and Type 1 specimen size (length of 80 mm, width of 10 mm, andthickness of 4 mm). Specimens are cut from the center of a multi-purposebar using a single tooth milling machine. The testing temperature is 23°C., −30° F., or −40° F. as reported below.

Unnotched Charpy Impact Strength: Unnotched Charpy properties are testedaccording to ISO Test No. 180 (technically equivalent to ASTM D256). Thetest is run using a Type 1 specimen (length of 80 mm, width of 10 mm andthickness of 4 mm). Specimens are cut from the center of a multi-purposebare using a single tooth milling machine. The testing temperature is23° C.

Izod Notched Impact Strength: Notched Izod properties are testedaccording to ISO Test No. 180 (technically equivalent to ASTM D256,Method A). This test is run using a Type A notch. Specimens are cut fromthe center of a multi-purpose bar using a single tooth milling machine.The testing temperature is 23° C.

Density and Specific Gravity. Density was determined according to ISOTest No. 1183 (technically equivalent to ASTM D792). The specimen wasweighed in air then weighed when immersed in distilled water at 23° C.using a sinker and wire to hold the specimen completely submerged asrequired.

Vicat softening temperature: Vicat Softening temperature is determinedaccording to method A, with a load of 10 N and according to method Bwith a load of 50 N as described in ISO Test No. 306 (technicallyequivalent to ASTM D1525), both of which utilized a heating rate of 50K/h.

Water absorption is determined according to ISO Test No. 62. The testspecimens are immersed in distilled water at 23° C. until the waterabsorption essentially ceases (23° C./sat).

Complex viscosity: Complex viscosity is determined by a Low shear sweep(ARES) utilizing an ARES-G2 (TA Instruments) testing machine equippedwith 25 mm SS parallel plates and using TRIOS software. A dynamic strainsweep was performed on a pellet sample prior to the frequency sweep, inorder to find LVE regime and optimized testing condition. The strainsweep was done from 0.1% to 100%, at a frequency 6.28 rad/s. The dynamicfrequency sweep for each sample was obtained from 500 to 0.1 rad/s, withstrain amplitude of 3%. The gap distance was kept at 1.5 mm for pelletsamples. The temperature was set at 310° C. for all samples.

Melt strength and melt elongation is performed on ARES-G2 equipped EVFfixture. The flame bar sample was cut as shown in FIG. 19. The same areaof flame bar was used for each run, in order to keep the crystallinityof test sample same and thus to minimize the variation betweenreplicates. A transient strain was applied to each sample at 0.2/s rate.At least triplicate run was done for each sample to obtain arepresentative curve.

Permeation Resistance: The fuel permeation studies were performed onsamples according to SAE Testing Method No. J2665. For all samples,stainless-steel cups were used. Injection molded plaques with a diameterof 3 inches (7.6 centimeters) were utilized as test samples. Thethickness of each sample was measured in 6 different areas. An O-ringViton@fluoroelastomer was used as a lower gasket between cup flange andsample (Purchased from McMaster-Carr, cat#9464K57, A75). A flat Viton®fluoroelastomer (Purchased from McMaster-Carr, cat#86075K52, 1/16″thickness, A 75) was die-cut to 3 inch (7.6 cm) OD and 2.5 inch (6.35cm) ID, and used as the upper gasket between the sample and the metalscreen. The fuel, about 200 ml, was poured into the cup, the cupapparatus was assembled, and the lid was finger-tightened. This wasincubated in a 40° C. oven for 1 hour, until the vapor pressureequilibrated and the lid was tightened to a torque 15 in-lb. The fuelloss was monitored gravimetrically, daily for the first 2 weeks followedby twice a week for the rest of the testing period. A blank run was donein the same manner with an aluminum disk (7.6 cm diameter, 1.5 mmthickness) and the result was subtracted from the samples. All sampleswere measured in duplicate. The normalized permeation rate wascalculated following an equilibration period. The permeation rate foreach sample was obtained from the slope of linear regression fitting ofdaily weight loss (gm/day). The normalized permeation rate wascalculated by dividing the permeation rate by the effective permeationarea and multiplying by average thickness of specimen. The averagepermeation rates are reported.

EXAMPLE 1

Materials utilized to form the compositions included the following:

-   -   Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide        available from Ticona Engineering Polymers of Florence, Ky.    -   Impact Modifier LOTADER® AX8840—a random copolymer of ethylene        and glycidyl methacrylate available from Arkema, Inc.    -   Crosslinking Agent: Terephthalic Acid    -   Disulfide: 2,2-dithiodibenzoic acid    -   Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the disulfide was fed usinga gravimetric feeder at barrel 6. Materials were further mixed thenextruded through a strand die. The strands were water-quenched in a bathto solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 1, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 1 Component Addition Point Sample 1 Sample 2 Lubricant main feed0.3 0.3 Disulfide barrel 6 1.0 Impact Modifier main feed 25.0 25.0Polyarylene Sulfide main feed 74.7 73.7 Total 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 2, below.

TABLE 2 Sample 1 Sample 2 Melt Viscosity (poise) 3328 4119 TensileModulus (MPa) 1826 1691 Tensile Break Stress (MPa) 43.73 44.98 TensileBreak Strain (%) 96.37 135.12 Std. Dev. 39.07 34.40 Notched CharpyImpact 61.03 53.00 Strength at 23° C. (kJ/m²)

Samples were annealed at 230° C. for 2 hours and re-tested for physicalcharacteristics. Results are provided in Table 3, below.

TABLE 3 Sample 1 Sample 2 Tensile Modulus (MPa) 1994.00 1725.00 TensileBreak Stress (MPa) 45.04 45.20 Tensile Break Strain (%) 58.01 73.76 Std.Dev. 6.60 4.78

As can be seen, Sample 2 exhibited better tensile elongation and lowermodulus before and after annealing. However, no improvement in impactstrength was seen, which is believed to be due to a chain scissionreaction between the disulfide and the polypropylene sulfide.

EXAMPLE 2

Materials as described in Example 1 were melt mixed using a Coperionco-rotating, fully-intermeshing, twin-screw extruder with an overall L/Dof 40 and ten temperature control zones including one at the die. A highshear screw design was used to compound the additives into a resinmatrix. The polyarylene sulfide, impact modifier and lubricant were fedto the main feed throat in the first barrel by means of a gravimetricfeeder. The disulfide was fed using a gravimetric feeder at variouslocations in the extruder; at the main feed throat, at barrel 4 andbarrel 6. The crosslinking agent was fed at barrel 6. Materials werefurther mixed then extruded through a strand die. The strands werewater-quenched in a bath to solidify and granulated in a pelletizer.

Comparative Samples 3 and 4 were formed of the same composition andcompounded by use of a different screw design.

TABLE 4 Addition Point 3 4 5 6 7 8 9 10 Lubricant main feed 0.3 0.3 0.30.3 0.3 0.3 0.3 0.3 Crosslinking barrel 6 — — 0.5 1.0 1.0 0.5 0.5 0.5Agent Disulfide main feed — — — — — 0.30 — — Disulfide barrel 4 — — — —— — 0.3 — Disulfide barrel 6 — — — — — — — 0.3 Impact main feed 15.015.0 15.0 15.0 10.0 15.0 15.0 15.0 Modifier Polyarylene main feed 84.784.7 84.2 83.7 88.7 83.9 83.9 83.9 Sulfide Total 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0

Following formation, tensile bars were formed and tested for a varietyof physical characteristics. Results are provided in Table 5, below.

TABLE 5 Sample Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8Sample 9 10 Melt 2423 — 2659 2749 2067 2349 2310 2763 Viscosity (poise)Density — 1.28 — 1.25 — — — — (g/cm³) Tensile 2076 2800 2177 2207 25511845 2185 2309 Modulus (MPa) Tensile 46.13 — 45.40 48.27 51.71 46.4747.16 47.65 Break Stress (MPa) Tensile 33.68 25 43.97 35.94 26.90 47.5140.85 63.85 Break Strain (%) Elongation 5.17 5 5.59 7.49 4.5 11.78 6.947.00 at Yield (%) Yield 51.07 52 50.76 51.62 59.63 51.07 52.56 51.88Stress (MPa) Notched 22.30 30 23.90 39.40 14.80 12.50 19.70 39.90 CharpyImpact Strength at 23° C. (kJ/m²) Notched 7.8 7 — 10 — — — 10.8 CharpyImpact Strength at −30° C. (kJ/m²) DTUL (° C.) — 100 — 102 — — — — Melt280 280 280 280 280 280 280 280 Temp. (° C.) Water — 0.05 — 0.05 — — — —absorption (%)

Samples were annealed at 230° C. for 2 hours and re-tested for physicalcharacteristics. Results are provided in Table 6, below.

TABLE 6 Sample Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8Sample 9 10 Tensile 2383 — 2339 2279 2708 2326 2382 2491 Modulus MPaTensile 52.70 — 53.96 53.11 61.10 56.74 54.81 55.25 Break Stress (MPa)Tensile 29.42 — 20.97 35.76 20.34 31.37 41.23 49.03 Break Strain (%)Std. 6.84 — 6.95 6.66 5.40 2.83 2.65 3.74 Dev.

As can be seen, the highest tensile elongation and highest impactstrength were observed for Sample 10, which includes both thecrosslinking agent and the disulfide added at the same point downstreamduring processing.

FIG. 20 illustrates the relationship of notched Charpy impact strengthover temperature change for Sample 3 and for Sample 6. As can be seen,the thermoplastic composition of Sample 6 exhibits excellentcharacteristics over the entire course of the temperature change, with ahigher rate of increase in impact strength with temperature change ascompared to the comparison material.

FIG. 21A is a scanning electron microscopy image of the polyarylenesulfide used in forming the sample 3 composition and the FIG. 21B is ascanning electron microscopy image of the polyarylene sulfide used informing the sample 6 composition. As can be seen, there is no clearboundary between the polyarylene sulfide and the impact modifier in thecomposition of FIG. 21B (sample 6).

Tensile bar test specimens of samples 3, 6, and 10 were immersed in 10wt. % sulfuric acid for 500 hours at either 40° C. or 80° C. Tensileproperties and impact properties were measured before and after the acidexposure. Results are summarized in Table 7 below.

TABLE 7 Sample 3 Sample 6 Sample 10 Initial properties Tensile Modulus(MPa) 2076 2207 2309 Tensile Break Stress (MPa) 46.13 48.27 47.65Tensile Break Strain (%) 33.68 35.94 63.85 Charpy notched impact 22.3039.40 39.90 strength at 23° C. (kJ/m²) Properties after 500 hoursexposure in sulfuric acid at 40° C. Tensile Modulus (MPa) 2368 2318 2327Tensile Break Stress (MPa) 48.83 48.48 48.53 Tensile Break Strain (%)10.99 28.28 30.05 Charpy notched impact 18.4 33.6 3539 strength at 23°C. (kJ/m²) Loss in Charpy notched impact 18 15 15 strength (%)Properties after 500 hour exposure in sulfuric acid at 80° C. TensileModulus (MPa) 2341 2356 2354 Tensile Break Stress (MPa) 49.61 48.0448.86 Tensile Break Strain (%) 10.60 19.88 26.32 Charpy notched impact9.2 31.0 34.0 strength at 23° C. (kJ/m²) Loss in Charpy notched impact59 21 15 strength (%)

The results in the change in Charpy notched impact strength over timeduring exposure to the acid solution at an elevated temperature areillustrated in FIG. 22. As can be seen, the relative loss of strength ofsamples 6 and 10 is much less than the comparison sample.

EXAMPLE 3

Materials as described in Example 1 were melt mixed using a Coperionco-rotating, fully-intermeshing, twin-screw extruder with an overall L/Dof 40 and ten temperature control zones including one at the die. A highshear screw design was used to compound the additives into a resinmatrix. The polyarylene sulfide, impact modifier and lubricant were fedto the feed throat in the first barrel by means of a gravimetric feeder.The crosslinking agent was fed using a gravimetric feeder at the mainfeed throat and at barrel 6. Materials were further mixed then extrudedthrough a strand die. The strands were water-quenched in a bath tosolidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 8, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 8 Addition Sample Sample Sample Sample Component Point 11 12 13 14Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking main — 0.5 1.0 — Agentfeed Crosslinking barrel 6 — — — 1.0 Agent Impact main 15.0 15.0 15.015.0 Modifier feed Polyarylene main 84.7 84.2 83.7 83.7 Sulfide feedTotal 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested fora variety of physical characteristics. Results are provided in Table 9,below.

TABLE 9 Sample Sample Sample Sample 11 12 13 14 Melt Viscosity (poise)2649 2479 2258 3778 Tensile Modulus (MPa) 2387 2139 2150 1611 TensileBreak Stress 46.33 49.28 51.81 42.44 (MPa) Tensile Break Strain 24.6222.60 14.45 53.62 (%) Std. Dev. 9.19 1.51 2.23 1.90 Notched Charpy 27.508.50 6.00 39.30 Impact Strength at 23° C. (kJ/m²) Std. Dev. 2.7 1.100.60 2.10

As can be seen, upstream feed of the crosslinking agent decreased theimpact properties of the composition, while downstream feed increasedthe tensile elongation by 118% and room temperature impact strength by43%.

EXAMPLE 4

Materials as described in Example 1 were melt mixed using a Coperionco-rotating, fully-intermeshing, twin-screw extruder with an overall L/Dof 40 and ten temperature control zones including one at the die. A highshear screw design was used to compound the additives into a resinmatrix. The polyarylene sulfide, impact modifier and lubricant were fedto the feed throat in the first barrel by means of a gravimetric feeder.The crosslinking agent was fed using a gravimetric feeder at barrel 6.Materials were further mixed then extruded through a strand die. Thestrands were water-quenched in a bath to solidify and granulated in apelletizer.

Compositions of the samples are provided in Table 10, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 10 Addition Sample Sample Sample Sample Component Point 15 16 1718 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.7 1.01.7 Agent Impact main 25.0 25.0 15.0 15.0 Modifier feed Polyarylene main73.7 73.0 83.7 83.0 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested fora variety of physical characteristics. Results are provided in Table 11,below.

TABLE 11 Sample Sample Sample Sample 15 16 17 18 Melt Viscosity (poise)4255 4198 2522 2733 Density (g/cm³) 1.2 — — — Tensile Modulus (MPa)1582.00 1572.00 2183.00 2189.00 Tensile Break Stress 45.59 46.29 48.9849.26 (MPa) Tensile Break Strain 125.92 116.40 66.13 48.24 (%) Std. Dev.19.79 9.97 15.36 7.80 Elongation at Yield (%) 23 — — — Yield Stress(MPa) 42 — — — Flex Modulus (MPa) 1946.00 1935.00 2389.00 2408.00Flexural Stress @3.5% 48.30 48.54 68.55 68.12 (MPa) Notched Charpy 55.6051.80 43.60 19.10 Impact Strength at 23° C. (kJ/m²) Std. Dev. 1.00 1.401.50 1.50 Notched Charpy 13 — — — Impact Strength at −30° C. (kJ/m²)Notched Charpy 13.30 12.10 11.26 8.70 Impact Strength at −40° C. (kJ/m²)Std. Dev. 1.50 0.90 0.26 0.50 DTUL (1.8 MPa) (° C.) 97.20 97.60 01.70100.90 Water absorption (%) 0.07 — — —

EXAMPLE 5

Materials as described in Example 1 were utilized except for thepolyarylene sulfide, which was Fortron® 0320 linear polyphenylenesulfide available from Ticona Engineering Polymers of Florence, Ky.Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide and impact modifier were fed to the feed throat inthe first barrel by means of a gravimetric feeder. The crosslinkingagent was fed using a gravimetric feeder at barrel 6. Materials werefurther mixed then extruded through a strand die. The strands werewater-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 12, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 12 Addition Sample Sample Sample Sample Sample Component Point 1920 21 22 23 Crosslinking barrel 6 — — — 0.1 0.2 Agent Impact main — 1.53.0 1.5 3.0 Modifier feed Polyarylene main 100.0 98.5 97.0 98.4 96.8Sulfide feed Total 100.0 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested fora variety of physical characteristics. Results are provided in Table 13,below.

TABLE 13 Sample Sample Sample Sample Sample 19 20 21 22 23 MeltViscosity 2435 2684 2942 2287 1986 (poise) Tensile Modulus 3208 32073104 3245 3179 (MPa) Tensile Break Stress 67.20 72.94 59.06 63.95 60.80(MPa) Tensile Break Strain 2.46 4.54 11.96 6.31 11.40 (%) Std. Dev. 0.321.11 1.24 2.25 3.53 Flex Modulus 13103.00 3173.00 303.100 3284.003156.00 (MPa) Flexural Stress 105.76 104.74 100.21 109.09 104.81 @3.5%(MPa) Notched Izod 2.90 5.20 5.60 4.10 4.30 Impact Strength at 23° C.(kJ/m²) Std. Dev. 0.40 0.40 0.40 0.20 0.20 DTUL (1.8 MPa) 105.60 104.00103.70 104.20 104.80 (° C.)

EXAMPLE 6

-   -   Materials utilized to form the compositions included the        following:    -   Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide        available from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier LOTADER® 4720—a random terpolymer of ethylene, ethylacrylate and maleic anhydride available from Arkema, Inc.

Crosslinking Agent: Hydroquinone

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at the main feed for samples 24 and 25and at barrel 6 for samples 26 and 27. Materials were further mixed thenextruded through a strand die. The strands were water-quenched in a bathto solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 14, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 14 Addition Sample Sample Sample Sample Sample Component Point 2425 26 27 28 Lubricant main feed 0.3 0.3 0.3 0.3 0.3 Crosslinking barrel6 — — — 0.1 0.2 Agent Crosslinking main feed — 0.1 0.2 — — Agent Impactmain feed 15.0 15.0 15.0 15.0 15.0 Modifier Polyarylene main feed 84.784.6 84.5 84.6 84.5 Sulfide Total 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 15, below.

TABLE 15 Sample Sample Sample Sample Sample 24 25 26 27 28 MeltViscosity 2435 2797 3251 2847 2918 (poise) Tensile Modulus 2222 21642163 2184 2145 (MPa) Tensile Break 52.03 45.17 46.53 45.47 46.39 Stress(MPa) Tensile Break 36.65 50.91 63.39 38.93 41.64 Strain (%) Std. Dev.9.09 14.9 11.88 7.62 10.42 Elongation at Yield 5.75 5.49 5.76 5.53 5.70(%) Yield Stress (MPa) 52.03 50.21 50.77 51.39 50.85 Flexural Modulus2358.00 2287.00 2286.00 2305.00 2281.00 (MPa) Flexural Stress 70.5168.25 68.03 69.23 68.23 @3.5% (MPa) Notched Charpy 29.80 44.60 50.6042.30 45.90 Impact Strength at 23° C. (kJ/m²) Std. Dev. 4.10 2.40 1.901.90 1.60 Notched Charpy 5.90 9.30 11.00 9.60 9.80 Impact Strength at−40° C. (kJ/m²) Std. Dev. 1.00 0.90 1.20 0.80 1.30 DTUL (1.8 MPa) 99.1093.90 98.20 100.10 99.00 (° C.)

EXAMPLE 7

Materials utilized to form the compositions included the following:

-   -   Polyarylene sulfide:        -   PPS1-Fortron® 0203 linear polyphenylene sulfide available            from Ticona Engineering Polymers of Florence, Ky.        -   PPS2-Fortron®0205 linear polyphenylene sulfide available            from Ticona Engineering Polymers of Florence, Ky.        -   PPS3-Fortron®0320 linear polyphenylene sulfide available            from Ticona Engineering Polymers of Florence, Ky.    -   Impact Modifier LOTADER® AX8840—a random copolymer of ethylene        and glycidyl methacrylate available from Arkema, Inc.    -   Crosslinking Agent: Terephthalic Acid    -   Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at barrel 6. Materials were further mixedthen extruded through a strand die. The strands were water-quenched in abath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 16, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 16 Addition Sample Sample Sample Sample Component Point 29 30 3132 Sample 33 Sample 34 Lubricant main 0.3 0.3 0.3 0.3 0.3 0.3 feedCrosslinking barrel 6 1.0 1.0 1.0 Agent Impact main 15.0 15.0 15.0 15.015.0 15.0 Modifier feed PPS1 main 84.7 83.7 feed PPS2 main 84.7 83.7feed PPS3 main 84.7 83.7 feed Total 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 17, below.

TABLE 17 Sample Sample Sample Sample Sample Sample 29 30 31 32 33 34Tensile 2292 2374 2250 2427 2130 2285 Modulus (MPa) Tensile Break 50.9250.18 49.18 53.22 48.01 48.08 Stress (MPa) Tensile Break 5.79 2.84 23.7934.73 23.55 45.42 Strain (%) Std. Dev. 0.99 0.18 11.96 4.01 18.57 18.94Flexural 2279.00 2382.00 2257.00 2328.00 2292.00 2294.00 Modulus (MPa)Flexural Stress 71.11 74.94 69.72 72.39 67.95 68.95 @3.5% (MPa) Notched5.70 3.70 9.10 12.80 19.40 45.40 Charpy Impact Strength at 23° C.(kJ/m²) Std. Dev. 0.90 0.70 0.80 1.00 2.70 7.70 Notched 3.00 2.50 5.105.00 5.10 8.00 Charpy Impact Strength at −40° C. (kJ/m²) Std. Dev. 0.700.30 0.60 0.30 0.40 1.00 DTUL 101.00 105.50 100.00 102.90 99.90 100.40(1.8 MPa) (° C.)

EXAMPLE 8

Materials utilized to form the compositions included the following:

-   -   Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide        available from Ticona Engineering Polymers of Florence, Ky.    -   Impact Modifier LOTADER® AX8840—a random copolymer of ethylene        and glycidyl methacrylate available from Arkema, Inc.    -   Crosslinking Agent: Terephthalic Acid    -   Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at barrel 6. Materials were further mixedthen extruded through a strand die. The strands were water-quenched in abath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 18, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 18 Addition Sample Sample Sample Sample Component Point 35 36 3738 Sample 39 Sample 40 Lubricant main 0.3 0.3 0.3 0.3 0.3 0.3 feedCrosslinking barrel 6 0.75 1.25 1.75 Agent Impact main 15.0 15.0 25.025.0 35.0 35.0 Modifier feed Polyarylene main 84.7 83.95 74.70 73.4564.70 62.95 Sulfide feed Total 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 19, below. Sample 39 wasnot injection moldable.

TABLE 19 Sample Sample Sample Sample Sample Sample 35 36 37 38 39 40Melt Viscosity 2323 2452 2955 3821 2025 5462 (poise) Tensile 2281 22982051 1721 — 1045 Modulus (MPa) Tensile Break 47.09 49.09 47.29 46.18 —39.81 Stress (MPa) Tensile Break 28.92 36.42 97.33 110.36 — 96.76 Strain(%) Std. Dev. 6.35 3.13 53.94 8.40 — 1.77 Elongation 5.28 8.58 36.00108.19 — 95.77 at Yield (%) Yield Stress 52.42 53.92 46.50 46.76 — 40.43(MPa) Flexural 2388.00 2349.00 2210.00 1750.00 — 1209.00 Modulus (MPa)Flexural Stress 71.52 71.70 63.15 50.52 — 34.41 @3.5% (MPa) Notched35.15 38.40 57.00 52.70 — 52.10 Charpy Impact Strength at 23° C. (kJ/m²)Std. Dev. 6.22 1.50 1.40 3.40 — 2.10 Notched 8.20 10.70 8.70 18.10 —14.10 Charpy Impact Strength at −30° C. (kJ/m²) Std. Dev. 1.50 1.60 0.200.90 — 0.80 Notched 7.26 9.20 8.00 16.80 — 12.47 Charpy Impact Strengthat −40° C. (kJ/m²) Std. Dev. 1.54 2.30 0.60 0.40 — 0.92 DTUL 99.90103.60 98.10 99.30 — 92.70 (1.8 MPa) (° C.) Water — — — — — 0.1absorption (%)

EXAMPLE 9

Materials utilized to form the compositions included the following:

-   -   Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide        available from Ticona Engineering Polymers of Florence, Ky.    -   Impact Modifier LOTADER® AX8840—a random copolymer of ethylene        and glycidyl methacrylate available from Arkema, Inc.    -   Crosslinking Agent: Terephthalic Acid    -   Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at barrel 6. Materials were further mixedthen extruded through a strand die. The strands were water-quenched in abath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 20, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 20 Addition Sample Sample Sample Sample Component Point 41 42 4344 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.11.25 1.25 Agent Impact main 15 20 25 30 Modifier feed Polyarylene main83.7 78.6 73.45 68.45 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 21, below.

TABLE 21 Sample Sample Sample Sample 41 42 43 44 Specific Gravity 1.251.20 1.15 1.20 (g/cm³) Tensile Modulus 2200 1600 1200 1700 (MPa) (50mm/min) Tensile Break 50 42 40 46 Strength (MPa) (50 mm/min) Elongationat 40 100 90 75 Break (%) (50 mm/min) Yield Stress (MPa) 55 42 40 48 (50mm/min) Yield Strain (%) 9 25 90 15 (50 mm/min) Flexural Modulus 22001700 1300 1900 (MPa) Flexural Strength 68 50 40 56 @3.5% (MPa) NotchedCharpy 40 55 50 50 Impact Strength at 23° C. (kJ/m²) Notched Charpy 1024 20 20 Impact Strength at −30° C. Unnotched Charpy Not Not Not NotImpact Strength at broken broken broken broken 23° C. DTUL (1.8 MPa) 102100 95 100 (° C.) Water absorption 0.05 0.07 0.1 0.05 (%) Vicatsoftening 270 270 270 270 temp. (A10N, ° C.) Vicat softening 200 160 110180 temp. (B50N, ° C.) Complex viscosity 79.994 289.27 455.19 — (0.1rad/sec. 310° C.) (kPa/sec)

Samples 41, 42, and 43 were tested to determine complex viscosity aswell as melt strength and melt elongation as a function of Henckystrain. As a comparative material, Sample 3 as described in Example 2was utilized. Samples 41, 42 and 43 were done at 310° C. and sample 3was done at 290° C. Results are shown in FIG. 23, FIG. 24, and FIG. 25.

EXAMPLE 10

Sample 42 described in Example 9 was utilized to form a blow molded 1.6gallon tank. The formed tank is illustrated in FIG. 26. Cross sectionalviews of the tank are presented in FIG. 27A and FIG. 27B. The formedtank has a good outer surface with regard to both visual inspection andfeel. As shown in FIG. 27A, an even wall thickness (about 3 mm) wasobtained and minimal sag was observed. As shown in FIG. 27B, thepinch-offs formed an excellent geometry.

EXAMPLE 11

Samples 41, 42, and 43 described in Example 9 were tested to determinepermeation of various fuels including CE10 (10 wt. % ethanol, 45 wt. %toluene, 45 wt. % iso-octane), CM15A (15 wt. % methanol and 85 wt. %oxygenated fuel), and methanol. Sample No. 4 described in Example 2 wasutilized as a comparison material. Two samples of each material weretested.

Table 22, below provides the average sample thickness and effective areafor the samples tested with each fuel.

TABLE 22 Average Sample Effective area Sample Thickness (mm) (m²) CE10Aluminum blank-1 1.50 0.00418 Aluminum blank-2 1.50 0.00418 Sample No.4-1 1.47 0.00418 Sample No. 4-2 1.45 0.00418 Sample No. 41-1 1.470.00418 Sample No. 41-2 1.49 0.00418 Sample No. 42-1 1.47 0.00418 SampleNo. 42-2 1.46 0.00418 Sample No. 43-1 1.45 0.00418 Sample No. 43-2 1.470.00418 CM15A Aluminum blank - 1 1.50 0.00418 Aluminum blank - 2 1.500.00418 Sample No. 4-1 1.48 0.00418 Sample No. 4-2 1.49 0.00418 SampleNo. 41-1 1.49 0.00418 Sample No. 41-2 1.50 0.00418 Sample No. 42-1 1.470.00418 Sample No. 42-2 1.48 0.00418 Sample No. 43-1 1.46 0.00418 SampleNo. 43-2 1.47 0.00418 Methanol Aluminum blank - 1 1.50 0.00418 Aluminumblank - 2 1.50 0.00418 Sample No. 4-1 1.49 0.00418 Sample No. 4-2 1.490.00418 Sample No. 41-1 1.49 0.00418 Sample No. 41-2 1.51 0.00418 SampleNo. 42-1 1.48 0.00418 Sample No. 42-2 1.47 0.00418 Sample No. 43-1 1.470.00418 Sample No. 43-2 1.48 0.00418

The daily weight losses for each material and each fuel are shown inFIGS. 28-30. Specifically, FIG. 28 shows the daily weight loss for thesamples during the permeation test of CE10, FIG. 29 shows the dailyweight loss for the samples during the permeation test of CM15A, andFIG. 30 shows the daily weight loss for the samples during thepermeation test of methanol.

The average permeation rates for each sample with each fuel are providedin Table 23. Note that Sample No. 43 takes a longer time to arrive atequilibrium, so the linear regression fitting was generated based ondata between days 42 and 65 for this material, while the linear regressfitting was generated for the other materials between days 32 and 65.For methanol, the linear regression fitting was generated based on databetween days 20 and 65, but with Sample No. 604, the methanol linearregression fitting was generated based on data between days 30 and 65.Some samples show negative permeability, which is because the weightloss of the sample was lower than that of the aluminum blank.

TABLE 23 Normalized Average Average permeation Normalized Permeation -Permeation - (g-mm/ permeation 3 mm 3 mm Sample day-m²) (g-mm/day-m²)thickness thickness CE10 Sample No. 0.06 0.05 ± 0.01 0.02 0.02 ± 0   4-1Sample No. 0.05 0.02 4-2 Sample No. 0.07 0.04 ± 0.04 0.02 0.01 ± 0.0141-1 Sample No. 0.01 0.00 41-2 Sample No. 0.06 0.06 ± 0   0.02 0.02 ±0   42-1 Sample No. 0.06 0.02 42-2 Sample No. 2020 2.51 ± 0.43 0.73 0.84± 0.14 43-1 Sample No. 2.81 0.94 43-2 CM15A Sample No. 0.49 0.18 ± 0.440.16 0.06 ± 0.15 4-1 Sample No. −0.13 −0.04 4-2 Sample No. 0.50 0.11 ±0.55 0.17 0.04 ± 0.18 41-1 Sample No. −0.27 −0.09 41-2 Sample No. −0.130.27 ± 0.58 −0.04 0.09 ± 0.19 42-1 Sample No. 0.68 0.23 42-2 Sample No.2.04 2.29 ± 0.35 0.68 0.76 ± 0.12 43-1 Sample No. 2.53 0.84 43-2Methanol Sample No. 0.37 0.25 ± 0.18 0.12 0.08 ± 0.06 4-1 Sample No.0.13 0.04 4-2 Sample No. 0.02 0.05 ± 0.05 0.01 0.02 ± 0.02 41-1 SampleNo. 0.08 0.03 41-2 Sample No. 0.28 0.25 ± 0.05 0.09 0.08 ± 0.02 42-1Sample No. 0.21 0.07 42-2 Sample No. 0.27 0.41 ± 0.2  0.09 0.14 ± 0.0743-1 Sample No. 0.55 0.18 43-2 The error was derived from the standarddeviation of duplicates in each sample.

These and other modifications and variations to the present disclosuremay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present disclosure. Inaddition, it should be understood the aspects of the various embodimentsmay be interchanged, either in whole or in part. Furthermore, those ofordinary skill in the art will appreciate that the foregoing descriptionis by way of example only, and is not intended to limit the disclosure.

What is claimed is:
 1. A component comprising a blow moldedthermoplastic composition, the thermoplastic composition including alinear polyarylene sulfide containing less than about 1 wt. % ofcross-raking units based on the total monomer units of the polyarylenesulfide, the thermoplastic composition further including a crosslinkedimpact modifier comprising the reaction product of a terephthalic acidcrosslinking agent and an epoxy-functionalized impact modifier, thethermoplastic composition exhibiting a permeation to a fuel or a fuelsource of lest than about 10 g-mm/m²-day or less as determined accordingto SAE Testing Method No. J2665.
 2. The component of claim 1, whereinthe blow molded thermoplastic composition has a notched Charpy impactstrength of greater than about 3 kJ/m² as determined according to ISOTest No. 197-1 at 23° C. and a tensile modulus of less than about 3000MPa as determined according to ISO Test No. 527 at a temperature of 23°C. and a test speed of 5 mm/min.
 3. The component of claim 1, whereinthe component is an automotive component.
 4. The component of claim 3,wherein the automotive component is a component of the fuel system, anexterior structure or a support structure for an automobile, or acomponent of an automotive exhaust system.
 5. The component of claim 4,wherein the automotive component is a fuel filter neck, or a fuel tank.6. The component of claim 1, wherein the component is a single layer ora multi-layer tubular component.
 7. The component of claim 6, whereinthe single layer or multi-layer tubular component is a flow line, ariser, or an air duct.
 8. The component of claim 1, wherein thethermoplastic composition has: an elongation at yield of greater thanabout 4.5% as determined according to ISO Test No. 527 at a temperatureof 23° C. and a test speed of 5 mm/min.
 9. The component of claim 1,wherein the polyarylene sulfide is polyphenvlene sulfide.
 10. Thecomponent of claim 1, wherein the thermoplastic composition furthercomprises a filler, a UV stabilizer, a heat stabilizer, a lubricant, acolorant, or a combination thereof.
 11. The component of claim 1,wherein the thermoplastic composition has a halogen content of less thanabout 1000 ppm.
 12. The component of claim 1, wherein a first section ofthe component comprises the thermoplastic composition, the first sectionbeing adjacent to a second section of a shaped product, wherein thesecond section does not comprise the thermoplastic composition.
 13. Thecomponent of claim 1, wherein the thermoplastic composition is free ofplasticizers.
 14. The component of claim 1, wherein the thermoplasticcomposition exhibits a permeation resistance to methanol at 40° C. ofless than about 1 g-mm/m²-day as determined according to SAE TestingMethod No. J2665.
 15. The component of claim 1, wherein thethermoplastic composition has a notched Charpy impact strength ofgreater than about 8 kJ/m² as measured according to ISO Test No. 179-1at a temperature of −30° C.
 16. The component of claim 1, wherein thethermoplastic composition has a tensile elongation at break of greaterthan about 10% as determined according to ISO Test No. 527 at atemperature of 23° C. and a test speed of 5 mm/min.
 17. The component ofclaim 1, wherein the thermoplastic composition has a tensile strength atbreak of greater than about 30 MPa as measured according to ISO Test No.527 at a temperature of 23° C. and a test speed of 5 mm/min.
 18. Thecomponent of claim 1, wherein the thermoplastic composition lids aflexuial muLlulus of less than about 2500 MPa as measured according toISO Test No. 178 at a temperature of 23° C. and a test speed of 2mm/min.
 19. The component of claim 1, wherein the thermoplasticcomposition has a deflection temperature under load of greater thanabout 80° C. as determined according to ISO Test No. 78 at 1.8 MPa. 20.The component of claim 1, wherein the thermoplastic composition has astrain at break greater than about 5% as measured according to ISO TestNo. 527 at a temperature of 23° C. and a test speed of 5 mm/min.
 21. Thecomponent of claim 1, wherein the thermoplastic composition meets theV-0 flammability standard at a thickness of 0.2 millimeters.
 22. Thecomponent of claim 1, wherein the epoxy-functionalized impact modifierincludes methacrylic monomer units.
 23. The component of claim 22, theepoxy-functionalized impact modifier further includes α-olefin monomerunits.
 24. The component of claim 1, wherein the thermoplasticcomposition exhibits a tensile elongation at break of about 50% or moreas determined in accordance with ISO Test No. 527 at a temperature of23° C. and at a speed of 50 mm/min.
 25. the component of claim 24,wherein the thermoplastic composition exhibits a tensile elongation atbreak of about 70% or more.